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Matou Kariya
Master of Berserker and Shinji's uncle. Severs ties with the Matou family some 10 years ago out of disgust. Childhood friend of Aoi Tohsaka's. Also was in love with her but gave up peacefully when she seemed to be happy accepting her engagement to Tokiomi.
Gets really pissed off when he finds out that Tokiomi gives Sakura to Zouken and then makes a deal with Zouken that he'll get the grail for him in exchange for Sakura's freedom. Since he never received training as a magus (has potential in comparison to Shinji and Shinji's father (whose name is Byakuya btw), he has to have worms implanted in him to boost his circuits and undergo really fast training for the coming war (result is shortenned life span and constantly weakenning body that's being eaten alive by the worm circuits).
Main target is Tokiomi.

Berserker
Kariya's Berserker. A black armored knight whose NP seems to be his own maryoku which lets him use ANY weapon he grabs as if it were a NP (even a cut-down telephone pole or the NP of some other hero). This lets him defend himself against Gilgamesh considerably well (grabs a weapon flung at him by Gil with his own hand and then uses it to parry a volley of 16 weapons) and push Saber back. Backside is the power load requirements for materialization (several times higher than other Servants) on Kariya (activated worm/circuits will also eat into his own body). Control (as in maintenance/power supply control) also seems to be unstable which causes Kariya to collapse as he's unable to get Berserker to dematerialize. Identity is unknown.


Waver Velvett
Future Lord El-Melloi II. Was a 19-year old student in the Clock Tower. Family line is only some 3 generations long. Came up with the revolutionary idea of emphasizing effort, experience, and knowledge over the typical magus approach of increasing power by increasing the potential of the heirs. Manuscript for the book he wrote got torn up by his teacher (typical student-teacher relationship, not the private master-pupil one) Caithness El-Melloi, a noble. So he gets pissed off at him and then hears about how El-Melloi will be participating in some competition for a Holy Grail in Japan. And then one day, Waver is entrusted with the artifact (a mantle) that El-Melloi is going to use to summon his Servant. Waver runs off with it and heads off to Japan where he summons.....

Rider
Iskandar, king of conquerors. Big guy. Not much more to say on his character other than what was said above. Would prefer to conquer the other Servants instead of defeat/destroy them and actually intervenes in what would have been a death match between Saber and Lancer (introducing himself by his real name followed by his class). Which provokes further trouble as his challenge for the other Servants to show themselves causes Gil to show up, which then causes Kariya to send Berserker over there too. Also happens to be the same guy that causes the whole incident to end without anybody dying. Has more than one Noble Phantasm. The first is the Gordius Wheel - Wheel of Heaven's Authority. Slices the air with his sword which causes a chariot run by two oxes to appear.
Described as a wild king that doesn't consider other people, but whose greed results in ultimately in the happiness of his people. Iskandar, the king of conquerors, who became a overlord while still a mortal. Gil, btw, is described as an absolute controller surpassing mortals.

Caithness El-Melloi
Master of Lancer. A noble in the Association that has the elements of water and wind.
Ends up coming anyway even though his catalyst was stolen. Really pissed off at Waver. A cruel person apparently. Regarded as being one of the two threatenning magi involved in the war at first by Kiritsugu.

Lancer
Diarmuid Ua Duibhne. Pretty nice guy. Not violent or berserk in the Cu Chulainn sense. Has two Noble Phantasms.
Gae Buidhe (Golden Rose of Mortality) and Ge Dearg (Crimson Rose of Exorcism). Latter acts as an anti-magic weapon that's able to dispell Invisible Air, go through Saber's armor, and Berserker's power. The former seems to have a Harpe/Gae Bolg like effect that makes whoever's hit by it unable to recover from the injury even after being healed. Saber gets hit by Gae Buidhe and has one of her arms disabled (this will continue until she settles her fight with Lancer). Lancer is about to finish her off but Iskandar intervenes.
Followed by some more chaos and Gilgamesh being Command Spelled back home, Berserker turns his attention to Saber. Lancer saves her but Caithness then uses a command spell on him that forces him to back-up Berserker to finish Saber off. Again, Iskandar butts in, forces Berserker to retreat, and threatens Caithness that he will join Saber against Lancer if he doesn't take back his order.

Uryuu Ryuunosuke
Psycho killer who got bored of the usual way of killing and was looking for some other ways of having fun. Like, following the instructions of what this book he found in his parent's place about summoning. He happens to murder an entire family, except for one kid, and uses their blood to fulfill the summoning ritual that was written in the book. He saves the kid btw, because he wants to feed the kid to the demon he's summoning. This happens to be in Fuyuki a little before the official start of the 4th war. Family, btw, happened to be descended from a line of mages (?) or at least people that definitely had circuits. Summons a Caster that goes by the name "Bluebeard" (in quotes).
A dumb nonserious guy that knows nothing about magic, heaven's feel or whatever. Or maybe just whacko.

Caster
"Bluebeard". Seems to be the typical evil mage. Goes by the theory that terror is best served by providing a moment of relief first. Acts like he's letting the little kid go, then summons a horde of snake-like monsters that eats the kid. When Uryuu sees this he goes: Wow, that is so COOL. Seems to know Saber personally and describes her as being the light of his life and what gave it meaning. Seems to have a good idea of how she personally came to ruin at the end of her life. Or at least thinks he does.

Tokiomi
Full of himself and a schemer. Has strong ties with the Church. The Tohsakas were hidden Christians yknow. One day, Risei has him meet with Kirei, whose command spells appeared 3 years before the war is supposed to start. Both of them arrange for Kirei's transfer into the Association as a pupil of Tokiomi (before even telling him what those marks were supposed to be) and plan to have him make sure that Tokiomi gets the grail. Thinks that Kirei was made a Master by the grail to provide Tokiomi with extra command spells + Servant. And just like Risei, thinks highly of Kirei's character and ability, without realizing how empty Kirei feels. Summons Gilgamesh using the fossilized skin of the first snake that shed its skin. Is having a headache over how difficult it is to get Gilgamesh act quietly/secretly. Generally is having Kotomine doing recon work with Assassin.

Gilgamesh
Gilgamesh without the letting his pants down bit, as Kinoko says. But still has a big head. Gets pissed off easily, first at Iskandar, then at Berserker, then at Tokiomi who forces Gil to return before he unleashes a full Gate of Babylon on Berserker. Doesn't like the whole 3 kings bit.

Kotomine Kirei
Master of Assassin. Not much more to say on him. Acts polite, has fun teasing Rin. Does whatever is expected of him but feels no fulfillment despite the praise. Learns a considerable amount of thaumaturgy from Tokiomi in 3 years. Assessed by Kiritsugu as being just a normal person that expends many times more effort than the average person, which is why he's able to accomplish a lot but not master anything truly. Has doubts about why he was chosen. Is extremely interested in Kiritsugu's way of living or true objective; a magus who easily throws away his pride as a magus and treats thaumaturgy on the same level as technology.

Assassin
A Hassan. Or Hassans. There seems to be multiple Hassans under Kotomine's control. One of them was killed by Gilgamesh to assess how many other Masters were observing the current situation. Another seems to be a female Hassan. Used as recon.

Irisviel
A bigger Ilya and the heroine of Fate Zero. Never left the Einzbern castle in Europe until she arrived in Fuyuki with Saber as her partner (at this point, Kiritsugu was working independently and had arrived in Fuyuki separately). Chooses the clothing that Saber is going to wear and also was informed of her back story. Plays a support role (healer) for Saber.

Kiritsugu
A person who feels it's a sin to be happy when he has to be cruel in order to reach whatever utopia he's aiming after. Came up with a theory of battle which makes use of what blind spot that magi have towards technology and their own arrogance in their own powers. Technology is inferior itself in performance, but magi seem to be understimating it significantly to the point that situations that a solder would be able to adapt to would catch them completely off-guard. Uses a Walther WA2000 semiautomatic sniper rifle, 90 cm long, which fires 300 Winchester Magnum rounds, and has a range of over 1000 meters. Also equipped with AN/PVS04 night scope and with modified Spector IR heat thermal scope (Kiritsugu discovered that body temperature changes after magic circuits are activated, so with research and training, he's able to read the status of magic circuits from the distribution in the thermal imagery; good for determining magi from other people and also seeing any opening that might be there after a magus releases maryoku). Other weapons include a M950, stun grenades, C2 pastic explosives, and finally a Thomspon Contender that works as his Mystic Code which fires normal bullets as well as special bullets containing parts of his pounded bone which works like semi-conceptual weapons; striking the magus origin of Kiritsugu into whatever it hits.

Hisau Maiya

Surprisingly didn't do much, other than the Kiritsugu assistant thing. Armed with an AUG Steyr.