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Due to recent changes to the rules of the coveted category, nine movies including 'The Artist' and 'Hugo' are eligible to enter the list.
Praised for his distinguished roles in 'The Tree of Life' and 'Moneyball', the actor is also chosen because of the 'depth and versatility of his performances'.
The October 9's episode also features Hugh Jackman as Daniel Radcliffe in a skit where Andy Samberg sports hair like Wolverine's.
Pitt looks sleek in a suit and tie regardless of his stubbly mustache and beard, while Jolie gets a bit kinky by wearing a gold wrist cuff attached to a chain and handbag.
Following Pitt's Billy Beane who believes that baseball's conventional wisdom is wrong, the fresh preview also sees Philip Seymour Hoffman's Art Howe speaking his line.
In the newly-unleashed preview, Pitt's Billy Beane is seen applying a new approach to create a more competitive baseball team.
In the film, the 43-year-old actor portrays Oakland A's manager Art Howe while Pitt plays the general manager of the team.
The actor ditches his graying beard to portray Billy Beane in the drama which is currently filmed in Los Angeles, California.
Amy Pascal from Sony Pictures Entertainment has placed 'Moneyball' into 'limited turnaround' because she found the re-written script by Steven Soderbergh was totally different from earlier scripts.