While the Ace Attorney series prefers using duos or trios, the investigation team from case 3-5 fits perfectly: Franziska (choleric), Edgeworth (melancholic), Godot (phlegmatic), and Gumshoe (sanguine).
Angry Birds: Black bird (choleric), white bird (melancholic), red bird (phlegmatic), and yellow bird (sanguine).
The four spirits of the Book of Prophecy in Avalon Code can be identified as this: Rempo (choleric), Ur (melancholic), Neaki (phlegmatic), and Mieli (sanguine).
In Blaze Union, the first five party members: Garlot (choleric), Jenon (melancholic), Medoute (phlegmatic), Siskier (sanguine), and Aegina (leukine). And after the party dynamics suffer an upheaval, things shake down like so: Gulcasa and Leon (choleric), Nessiah (melancholic), Baldus (phlegmatic), Emilia (sanguine), and Aegina is... still leukine.
Borderlands: Mordecai (melancholic), Lilith (phlegmatic), Roland (choleric), Brick (sanguine)
Borderlands 2: Axton (sanguine with a bit of choleric), Maya (melancholic), Salvador (choleric), Zer0 (phlegmatic). With DLC, there's also Gaige and Krieg, who are Sanguine and Choleric respectively.
Hyperion: Handsome Jack (choleric), Mr. Blake (melancholic), Professor Nakayama (sanguine), Angel (phlegmatic)
Catherine, in terms of Vincent and his three bros that he hangs out with at the Stray Sheep. Orlando (choleric), Jonny (melancholic), Vincent (phlegmatic), and Toby (sanguine).
Melancholic: Hinata, Koizumi, Pekoyama and Gundam.
Phlegmatic: Komaeda, Nanami and Sonia.
Leukine: Tsumiki.
The four playable characters of Drakengard, though at times they muddle about with their humors, tend to fall into distinct ones: Arioch (sanguine), Caim (choleric), Leonard (melancholic), and Seere (phlegmatic).
The Chosen Four of EarthBound: Ness (choleric), Poo (melancholic), Jeff (phlegmatic), and Paula (sanguine).
Fate/stay night has Rin/Archer (choleric), Shirou/Saber (melancholic), Sakura (phlegmatic), and Rider (leukine).
Final Fantasy V is the definition of this trope, right down to the characters representing the same elements for each of the 4 crystals. Bartz (wind — sanguine), Faris (fire — choleric), Cara (earth — melancholic), and Lenna (water — phlegmatic).
Final Fantasy IX's first party: Steiner (choleric), Vivi (melancholic), Garnet (phlegmatic), and Zidane (sanguine).
Front Mission: The members of Carrion Crow seem to fit an ordinary Ensemble and a Combo Ensemble, two each, rather neatly:
Alder and Gentz (choleric), Commander Lloyd/custom name and Paul (melancholic), Hans and Bobby (phlegmatic), Peewee and Porunga (sanguine), and Frederick and Ralph (leukine).
Keith and Gregorio (sanguine/choleric), Natalie and Maury/Molly (melancholic/choleric), J.J. and Yeehin (melancholic/phlegmatic), and Sakata and Yang Meihua (sanguine/phlegmatic).
Gears of War's Delta Squad are like that: Marcus Fenix (choleric), Damon Baird (melancholic), Dominic Santiago (phlegmatic), and Augustus Cole (sanguine).
Grand Theft Auto IV: The four main characters fit: Brucie (choleric), Niko (melancholic), Little Jacob (phlegmatic), and Roman (sanguine).
The female leads of the visual novel G-Senjou no Maou are a picture-perfect example: Haru (choleric), Mizuha (melancholic), Tsubaki (phlegmatic), and Kanon (sanguine).
The playable characters of Kirby's Return to Dream Land. King Dedede (choleric), Meta Knight (melancholic), and Bandana Dee (phlegmatic), and Kirby (sanguine).
Both Left 4 Dead and Left 4 Dead 2 star a four-man (or, technically, three-man and one-woman) band. In the first: Francis (choleric), Bill (melancholic), Zoey (phlegmatic), and Louis (sanguine). In the second, Coach, Nick, Rochelle, and Ellis for the most part fill those roles respectively, though Ellis is the most clean-cut/consistent.
Due to the author being interested with the subject, MARDEK RPG does this. The author believes everyone has a primary and a secondary temperament, though. Perhaps the clearest ingame example is Legion: a construct created by an inventor. It was animated with dark magic, with the inventor saying the incantation - due to his stuttering, though, four souls entered the body instead of one - one for each temperament.
Mass Effect 2 has the starting four. Shepard (choleric), Miranda (melancholic), Jacob (phlegmatic), and Joker (sanguine).
Mass Effect 1 and Mass Effect 3 squads are often comprised this way: Shepard (choleric), Garrus (melancholic), Liara (phlegmatic), and Tali (phlegmatic). Likewise, Ashley (sanguine) and Kaiden (neutral phlegmatic).
Mega Man (Classic series): Forte/Bass (choleric), Proto Man/Blues (melancholic), Mega/Rock Man (phlegmatic), and Duo (sanguine).
Mega Man Battle Network: Lan and Gutsman.EXE (choleric), Mayl and Glyde.EXE (melancholic), Megaman.EXE (phlegmatic), Yai and Roll.EXE (sanguine), and Dex (leukine).
And later on, Dex is choleric (like his Navi); Chaud is melancholic (like his Navi); Mayl is phlegmatic (and so is Megaman.Exe, still); Yai is sanguine (like her Navi, still); and Lan is leukine.
Mega Man X: The sensitive, conscientious X (melancholic), Zero who does what X can't (choleric), the polite and fatherly Signas (phlegmatic), and the adventurous wise-guy Axl (sanguine).
Among the villains: Vile has nothing but choleric faults (and yikes!!); Lumine is phlegmatic; Dynamo is sanguine; and Sigma is leukine.
X-Hunters, counting Vile as the solo X-Hunter in his own right: Vile (choleric), Agile (melancholic), Serges (phlegmatic), and Violen (sanguine).
Capcom never made clear whether classic Mega/Rock Man is the same Mega Man as X. If they are the same, Mega Man underwent a major temperament change. note Some may argue that the melancholic temperament simply got brought to light more clearly as Mega Man got infused with human feelings.
Among the Four Guardians: The self-centered but playful Leviathan (choleric), the polite-but-confrontational Phantom (melancholic), the reliable and civil Harpuia (phlegmatic), and the encouraging but Trigger Happy Fefnir (sanguine).
Of the melancholic hero X a duplicate was made, who turned out more choleric than melancholic and not even remotely mature, scarcely one thing like the original X.
Evil trio of Zero 3: With what little personality he's shown to have, Omega seems to be phlegmatic/sanguine (opposite Copy-X); Weil seems to be leukine.
The Beauty and the Beast unit in Metal Gear Solid 4 applies: Raging Raven (choleric), Crying Wolf (melancholic), Screaming Mantis (phlegmatic), and Laughing Octopus (sanguine).
Nazi Zombies: Tank (choleric), Takeo (melancholic), Nikolai (phlegmatic), and Richtofen (sanguine).
Nier features has something of this as well. Nier (choleric), Emil (melancholic), Grimoire Weisse (phlegmatic), and Kaine (sanguine).
Judging by their programmed natures, the Pac-Man ghosts: Pinky is choleric (chases and ambushes); Inky is melancholic (cautious); Clyde is phlegmatic/leukine (indifferent and random); and Blinky is sanguine (cocky, always chases).
Intentionally invoked in Planescape: Torment. In the end game, you meet up with three copies of yourself, who are the good incarnation (melancholic), crazy incarnation (sanguine) and pragmatic incarnation (choleric). The character of the protagonist depends on how you've been playing him, but he does start out as phlegmatic.
Kanto: Lt. Surge and Blaine (choleric), Sabrina and Janine (melancholic), Brock and Erika (phlegmatic), and Misty and Blue (sanguine).
Johto: Chuck and Clair (choleric), Morty and Pryce (melancholic), Falkner and Jasmine (phlegmatic), and Bugsy and Whitney (sanguine).
Hoenn: Flannery and Winona (choleric), and Norman and Juan (melancholic), Roxanne and Lisa/Tate (phlegmatic), and Brawly and Watson (sanguine).
Sinnoh: Crasher Wake and Byron (choleric), Fantina and Volkner (melancholic), Roark and Maylene (phlegmatic), and Gardenia and Candice (sanguine).
Unova: Clay, Lenora and Burgh (choleric); and Drayden and Marlon (melancholic), Cheren, Cillian/Cress/Chilli and Elesa (phlegmatic); and Roxie and Skyla (sanguine).
Similarly, the Elite Four:
Kanto: Lance (choleric), Agatha (melancholic), Bruno (phlegmatic), and Lorelei (sanguine).
Johto: Karen (choleric), Koga (melancholic), Bruno (phlegmatic), and Will (sanguine).
Hoenn: Sidney (choleric), Drake (melancholic), Glacia (phlegmatic), and Phoebe (sanguine).
Sinnoh: Flint (choleric), and Lucien (melancholic), Bertha (phlegmatic), and Aaron (sanguine).
Unova: Marshal (choleric), Caitlin (melancholic), Grimsley (phlegmatic), and Shauntal (sanguine).
As well as the various Pokemon League Champions: Blue & Lance (choleric), Cynthia & Alder (melancholic), Steven & Wallace (phlegmatic), and Iris (sanguine).
The crew in Saints Row 2 match up with this perfectly:
Johnny Gat is sanguine - he's happy when he's killing people or going to kill people.
The Boss, regardless of the voice you use, is very choleric, and tends to explode when questioned or fucked with.
Pierce is melancholic, and humour involving him tends to make fun of his elaborate plans and high professional standards clashing with the extreme personalities of the rest of the group.
Shaundi is very, very phlegmatic, what with being an archetypical laidback stoner.
Carlos is a mild leukine.
While in Saints Row 3, the group shift in some unusual ways:
Shaundi shifts radically from leukine to choleric, running on pure anger from start to finish.
Newcomer Oleg has some strong phlegmatic and leukine elements, but is mostly melancholic, becoming the key planner and thinker of the group.
The Boss is left, oddly enough, as the phlegmatic one; unlike in Saints Row 2, The Boss spends much more of the game haplessly reacting to the wild fortunes of fate thrown around him or her.
Pierce has become significantly more sanguine, a happy-go-lucky gladhander.
Star Wars Republic Commando: The four Clone Commandos of Delta Squad are this. Delta-38, "Boss", is choleric, showing good leadership instincts. Delta-07, "Sev", is melancholic, being the Cold Sniper of the group and showing great care to place each round for maximum effenciency. Delta-40, "Fixer", is phlegmatic, being, as Taun We put it, "A pure and uncomplicated soldier." Delta-62, "Scorch", is sanguine, showing much enjoyment in blowing the CIS forces apart.
In Street Fighter II, the four members of Shadaloo: Balrog (choleric), Sagat (melancholic), M. Bison (phlegmatic), and Vega (sanguine).
Suikoden III has three groups. The main characters: Chris (choleric), Thomas (melancholic), Geddoe (phlegmatic), and Hugo (sanguine). Duke's group: Duke (choleric), Nicholas (melancholic), Gau (phlegmatic), and Elaine (sanguine). Luc's group: Luc (melancholic), Sara (phlegmatic), Yuber (sanguine),and Albert (leukine).
In the Super Mario Bros. series and its Wario Land spinoff, the Mario Brothers and their parallels can form this schema: Wario (choleric), Mario (melancholic, but not brooding or depressive), Waluigi (phlegmatic), and Luigi (sanguine).
Count Bleck's Five-Bad Band in Super Paper Mario: O'Chunks (choleric), Nastasia (melancholic), Mimi (phlegmatic, but with a good dose of Ax Crazy), and Dimentio (sanguine).
The ATX Team in Super Robot Wars. At first the lineup is Sanger (choleric), Bullet (melancholic), Kyosuke (phlegmatic), and Excellen (sanguine). Later, Kusuha was drafted into the team as the leukine. Later on, Sanger leaves, and Kyosuke takes on the choleric mantle; and when Lamia enters, she takes on the phlegmatic mantle.
The Colour Tuesday: Alex is the hotheaded driver of the story (choleric). Kyle is the determined and selfless (melancholic). Bella is a slightly airy Cloudcuckoolander (sanguine). Chadd, the last permanent cast member, is a born follower (phlegmatic).
The Team Fortress 2 classes can be seen throughout the spectrum: Scout (choleric), Soldier (sanguine-choleric), Pyro (sanguine), Demoman (choleric-melancholic), Heavy (leukine, leaning choleric), Engineer (phlegmatic), Medic (phlegmatic-sanguine), Sniper (melancholic), Spy (melancholic-phlegmatic)
Tsukihime has Akiha (choleric), Ciel/Kohaku (sanguine facade but actually melancholic), Hisui (phlegmatic), and Shiki/Arcuied (sanguine).
Virtue's Last Reward: Dio and Tenmyouji (choleric), Alice and K (melancholic), Phi and Quark (phlegmatic), Sigma and Clover (sanguine), and Luna (leukine).