Shuya's closest friends before the program begins in Battle Royale fit into this. Shuya (sanguine), Shinji (choleric), Hiroki (melancholic), and Yoshitoki — killed before we get to learn much about him — seems to be phlegmatic.
The eponymous band in BECK fits this even better than the Five-Man Band pattern: Chiba (choleric), Taira (melancholic), Koyuki (phlegmatic), Saku (sanguine), and Ryusuke (leukine).
Tai (choleric), Matt (melancholic), Izzy (phlegmatic), TK (sanguine), and Joe (leukine).
Also the four Dark Masters fit this trope: The leading element Piedmon (choleric), the cold and calculating Evil Genius Machinedramon (melancholic), pragmatic Metalseadramon (phlegmatic) who's a good boss towards his minions as long as they don't fail him; and Puppetmon, with his Hot-BloodedPsychopathic Manchild demeanor (sanguine).
Elfen Lied: Lucy/Kaede (melancholic), Kohta (sanguine), Nana (phlegmatic), Yuka (choleric), and Mayu (leukine).
Although there are six main characters, this can work for Et Cetera, too: Fino (choleric), Benkate (melancholic), Baskerville (phlegmatic), Mingchao (sanguine), and Alternate and Yaghi (leukine). Mingchao can also be seen as melancholic while Benkate is sanguine.
Yzak (choleric), Athrun (melancholic), Dearka (phlegmatic), and Nicol (leukine). The four main leads as well with Kira and Athrun being phlegmatic and melancholic, respectively, Cagali being choleric and Lacus being sanguine.
The Minerva pilots in Gundam Seed Destiny possess two temparents: Shinn (both sanguine and melancholic), Athrun (choleric and melancholic), Ray (both melancholic and phlegmatic), and Lunamaria (sanguine and phlegmatic).
Gundam Wing: Heero Yuy (melancholic), Duo Maxwell (sanguine), Trowa Barton and Quatre Winner (phlegmatic, leukine), and Chang Wu Fei (choleric).
The Shuffle Alliance from Mobile Fighter G Gundam: Domon Kasshu (choleric), George DeSand (melancholic), Argo Gulskii (phlegmatic), and Chibodee Crockett and Sai Saici (sanguine).
Gurren Lagann — Early episodes: Yoko (choleric), Simon (melancholic), Leeron (phlegmatic), and Kamina (sanguine).
The four main boxers from Hajime No Ippo fit this well: Takamura (both choleric and sanguine), Aoki (melancholic), Kimura (phlegmatic), and Ippo (sanguine).
Inazuma Eleven has the managers fit into the arrangement perfectly: Natsumi (choleric), Fuyuka (melancholic), Aki (phlegmatic), and Haruna (sanguine).
K-on! has a slight variation: Yui (sanguine/phlegmatic), Ritsu (choleric/sanguine), Mugi (melancholic), and Mio (phlegmatic).
KamenRider Den-O's four Imagin: Momotaros (choleric), Urataros (melancholic), Kintaros (phlegmatic), and Ryutaros (sanguine).
The main cast of Katekyo Hitman Reborn!: Tsuna (phlegmatic), Gokudera (choleric), Yamamoto, Lambo and Ryohei (sanguine), Hibari (melanchonic), Mukuro (sanguine/choleric), and Chrome (leukine).
Keroro Gunsou follows the 5-humor style: Giroro (choleric), Dororo (melancholic), Kururu (phlegmatic), Tamama (sanguine), and Keroro (leukine).
Lucky Star: Kagami (choleric), Miyuki (melancholic), Tsukasa (phlegmatic), and Konata (sanguine). (None of the main characters qualify as Leukine).
Lupin III: It's because the characters have a consistent interaction that makes them function in nearly any setting or plot.
Sanguine: Lupin and Fujiko (when she's also an Action Girl) are the most extroverted cast members, and pretty self-indulgent, too. They love showing off, and getting people to do what they want.
Choleric: Zenigata is obsessed with the success of arresting Lupin. To the point where he will allow Fujiko and others to escape, for a chance at capturing Lupin. Even when the character is more mature, he is as Hot-Blooded as Lupin, and will instruct his subordinates to follow his instructions exactly. It's a good thing that when he does have subordinates, they're intensely loyal to him, or he'd be considered a Bad Boss.
Melancholic: The brooding Jigen, and his eternal slouch, is an example of a melancholic who has learned how to relax. When he's ""on the job", his hard-working and detached nature come to the fore.
Phlegmatic: Goemon, whose introversion is done as a part of training, does not need to be around other people for his training, but does so for the socialization.
Leukine: Whatever Damsel in Distress is around, including Fujiko, if the writers forgot her spunk.
Asuna (choleric), Setsuna (melancholic), Yue (phlegmatic), Kuu (sanguine), and Nodoka and Konoka (leukine).
The four sports stars include Yuna (choleric), Ako (melancholic), Akira (phlegmatic), and Makie (sanguine).
Monster: Eva (choleric), Tenma (melancholic), Johan (phlegmatic), and Anna/Nina (sanguine).
Team Kakashi in Naruto: Sakura (choleric), Sasuke (melancholic), and Naruto (sanguine). Kakashi was also melancholic, as he was the "Sasuke" of his own three-man team as a kid, although he's currently phlegmatic. His partners (the "Naruto" and the "Sakura", respectively) were sanguine Obito and leukine Rin.
The Four Main Konoha Girls: Sakura (Choleric), Ino (Melancholic), Hinata (Phlegmatic) ,Tenten (Sanguine).
A good example is Neon Genesis Evangelion: Asuka/Mari (choleric), Ritsuko/Gendo (melancholic), Shinji/Rei (phlegmatic), and Misato/Kaji (sanguine). You could actually also fit in Kaworu here as phlegmatic since he seemingly has absolutely no internal turmoil whatsoever at all. Of course, he only appears once (and when he does appear, Asuka is unconscious) so he doesn't completely count.
Although everyone in Ookiku Furikabutte gets his/her turn to shine, the story tends to focus on four core members of the baseball team: Hanai (choleric), Abe (melancholic), Mihashi (phlegmatic), and Tajima (sanguine).
Saiyuki also has two. For the Sanzo party: Sanzo (choleric), Hakkai (melancholic), Gojyo (phlegmatic), and Goku (sanguine). For Kougaiji's group: Kougaiji (choleric) and Lirin (sanguine). Yaone and Dokugakuji switch off between melancholic and phlegmatic, although neither of them is actually lazy.
Chiri (choleric), Itoshiki-sensei (melancholic), Nami (phlegmatic), and Kafuka (sanguine).
Also in the show: Kuniya (choleric), Aoyama (melancholic), Jun (phlegmatic), and Haga (sanguine).
Kaere (choleric), Abiru (melancholic), Harumi/Kiri/Matoi/Other relatively sane characters (phlegmatic), and Maria (sanguine).
School Rumble's main girls: Mikoto (choleric), Eri (melancholic), Akira (phlegmatic), and Tenma (sanguine).
The Slayers characters fit perfectly into these categories, with the Choleric Lina, Phlegmatic Gourry, Sanguine Amelia, and Melancholic Zelgadis. Any of their secondary allies, Sylphiel in particular, also fit into the Leukine temperament.
Soul Eater: Maka is choleric, Soul is phlegmatic, Death the Kid is melancholic, Tsubaki and Liz are leukine note Of course, Liz can be a little bit choleric herself., Black☆Star and Patti are sanguine.
Four Swords Plus'' manga by Akira Himekawa takes a literal spin with this trope by dividing Link into four different entities with personality traits that reflect the color tunic each is wearing: Green is melancholic, Red is sanguine, Blue is choleric and Purple is phlegmatic.
The flash animations by Hadouken Dude took this to absolutely hilarious levels, with Green Link as the melancholic (experienced/exasperated/anal-retentive) one, Blue Link being the phlegmatic (calmer/rational/lazy) one, Red Link as the choleric (severe testosterone imbalance/lack of foresight) one, and Purple Link being the sanguine (along for the ride/accused of being gay because of personality and color) type.
Five-temperament ensemble in Tokyo Mew Mew: Ichigo, although not happy about leading at first, accepting her responsibility later on (choleric); Minto (melancholic), Retasu (phlegmatic), the Genki Girl Bu-ling (sanguine), and Zakuro (leukine).
Trigun more often averts this trope in favor of the Lone Hero or the Power Trio. Adding Wolfwood to the cast has a subtractive effect instead, generating a duo dynamic that leaves Meryl and Millie on the sidelines. When they participate equally they fit the four temperaments: Meryl (choleric), Vash (melancholic, though pretending to be sanguine), Wolfwood (phlegmatic), and Millie (sanguine).
The four aunts in Umineko no Naku Koro ni: Eva (choleric), Natsuhi (melancholic), Kyrie (phlegmatic), and Rosa (sanguine). Probably works with the uncles and cousins too. There are two different ways to categorize the Higurashi girls. The first is — though actually works well no matter who is put in choleric position — Shion (choleric), Rika (melancholic), Satoko (phlegmatic), and Rena (sanguine). Alternately, if you wanted to include Keiichi, the pattern shifts to Keiichi (choleric), Rika (melancholic), Mion - phlegmatic, Rena (sanguine), and Satoko - leukine. Alternately, if you wanted to just do the girls, just replace Keiichi with Shion.
In the original Weiss Kreuz: Aya (choleric), Omi (melancholic), Youji (phlegmatic), and Ken (sanguine).
In Wolf's Rain: Tsume (choleric), Kiba (melancholic), Toboe (phlegmatic), and Hige (sanguine).
Yes! Pretty Cure 5 tries to throw us off by having four temperaments among five characters—both Nozomi and Urara are sanguine. Rin is choleric, Komachi is phlegmatic (though not lazy by any stretch), and Karen is melancholic.
In Fresh Pretty Cure!: Love is sanguine, Miki is choleric, Inori is more likely Phlegmatic, and Setsuna is a mix of melancholic and leukine.