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It's obvious the film Civil War will be much smaller then the comic, due to the much smaller list of characters. Even though the MCU has a much smaller group of characters, I still doubt they'll all be used. But in a perfect world where all characters are used who's going to side with whom?
On Captain Americas side:
Black Widow, Falcon, Winter Soldier, Ant-Man, Hawkeye, MockingBird, Black Panther, Spidey, Quicksilver, Nick Fury, Thor, Luke Cage, Daredevil, Jessica Jones, Iron Fist, Sif, Warriors Three, Quake, Calvin, Phil Coulson, Fitz and Simmons,
Iron Mans Side:
War Machine, Vision, Scarlett Witch, Hulk, Deathlok, Hellcat, Rescue, Wasp, Hank Pym, Maria Hill, Gonzales, SHIELD, Military, Government, Iron Man Legion, General Ross and Talbut, Abomination, Absorbing Man, Kingpin, Baron Zemo
What we'll most likely see in the movie:
Bucky, Widow, Falcon, Hawkeye, Scarlet Witch, Nick Fury, Sharon Carter
War Machine, Vision, Ant-Man, Maria Hill, General Ross, SHIELD,
Spidey: Start on Tony's then move to Steve's
Black Panther: Help both sides