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Ultimate Avengers is the first of eight direct-to-video features from Marvel Animation and Lions Gate Home Entertainment, creating MLG Productions for this purpose. It was originally released February 21, 2006 and was the first animated feature to have a sequel with Ultimate Avengers II. The film is a mostly faithful adaptation of the first storyarc of The Ultimates. The animated features were created to do the things the live action films could not, and this story was chosen to be a superhero version of The Dirty Dozen.

Following Hitler's defeat, Captain America (Justin Gross) leads an attack on a Nazi stronghold housing a superweapon. There he fights against Herr Kleiser (Jim Ward) and his alien comrades to stop a nuclear missile headed to Washington, D.C.. Captain America rides the missile and destroys it, which destroys an alien ship, but falls into the Atlantic Ocean. Sixty years later, a S.H.I.E.L.D. submarine headed by Nick Fury (Andre Ware) and Betty Ross (Nan McNamara) find the soldier's body. They bring him back to the Triskelion for study by the super soldier program's head Dr. Bruce Banner (Michael Massee). However, Steve wakes up and fights his way out but stops when he sees the modern New York City.

Meanwhile, the aliens attack a S.H.I.E.L.D. satellite prompting the oversight committee to force Fury to abandon the super soldier program, which has not been providing results, and starting the Avenger program despite Fury's objections. Fury and Black Widow (Olivia d'Abo) go to Tony Stark (Marc Worden) seeking information on Iron Man, who denies any involvement in the armored hero. The two then recruit Wasp (Grey Griffin), who only joins if her husband Giant Man (Nolan North) joins. Fury and Giant Man find Iron Man and try to recruit him, but he prefers to be alone. At the same time, Steve tries to reconnect with his old life but finds his old neighborhood completely different and his girlfriend Gail married to his friend Bucky who have grown old together. Fury talks Steve into joining the team and go to recruit Thor (David Boat). However, the Asgardian dislikes Fury and refuses.

At the team's first meeting, which Iron Man joins, Fury explains that the aliens are Chitauri and have been around since World War II. S.H.I.E.L.D. has some of their debris, which they call vibranium, that is seemingly indestructible. Steve is given command of the team and tasked with stopping the aliens. Later, Bruce confides in Steve that he accidentally became Hulk (Fred Tatasciore) because he wanted to be like him. When a Chitauri soldier attacks a S.H.I.E.L.D. base the team is sent after it. Captain America tries to lead but the civilian members refuse to listen to orders and the team fails. Fury berates them all and the team goes their separate ways.

Later, Betty discovers that Bruce wasn't working on the super soldier program, just on controlling Hulk. When confronted, Bruce uses a formula transforming into the jade giant but retaining control. At that time, the Chitauri launch an assault on the Triskelion. S.H.I.E.L.D. fails to hold them off but Hulk, Thor, and the Avengers appear stopping the aliens. Unfortunately, Bruce looses control and attacks the team. Hulk easily overpowers their combined might, until a combination of tranquilizers and Betty manage to calm him down. Afterwards, Bruce is put in a cell. Black Widow arranges to have Gail talk with Steve for peace of mind. The media dubs the team the Avengers while they have a feast in honor of Steve's leadership.

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