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Ifans will join Andrew Garfield (Peter Parker/Spider-Man) and Emma Stone (Gwen Stacy) in the project.
Amy Pascal, co-chairwoman of Sony Pictures Entertainment, and Matt Tolmach, president of Columbia Pictures, announced Ifan's casting today, reports Coming Soon.
"We have been very fortunate to attract some of the best actors working today to play the villains in the Spider-Man movies, and it is exciting to see that trend continue with Rhys Ifans," said Tolmach.
He added: "After seeing his performance in our upcoming film Anonymous, we're in awe of his talent and think he's the perfect choice to take on this role."
Director Marc Webb added: "What sets the Spider-Man villains apart is the complexity of their relationships with Peter Parker. Rhys's incredible ability to embody both warmth and rage makes him the ideal choice for this character."
The filmmakers did not reveal the name of Ifans's role.
Webb's Spider-Man movie is scheduled to arrive in 3D and conventional cinemas on July 3, 2012.
> Click here to watch our recent interview with Rhys Ifans
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