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The pair will reportedly play villains in the Jon Favreau-helmed project, due to begin shooting this spring.
Rourke, currently starring in The Wrestler, would portray a heavily-tattooed Russian arms dealer who battles Iron Man wearing a nuclear-powered suit of armour.
Frost/Nixon star Rockwell, who was an early candidate to play Iron Man, would take the role of multi-billionaire businessman Justin Hammer, a rival industrialist of Tony Stark, the hero's alter ego.
Justin Theroux has been hired to pen the script but Marvel bosses are keeping a tight lid on the storyline.
Original movie stars Robert Downey Jr. and Gwyneth Paltrow are both expected to return but Don Cheadle will replace Terrence Howard in the role of Jim Rhodes.
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