Joining them on the judging panel will be Zach Braff, Aaron Eckhart, Justin Bartha, Selma Blair, Peter Facinelli, Cheryl Hines and Whoopi Goldberg.
Their civic duty to the independent film community involves being holed up in screening rooms and together choosing their favorite entries – with 12 narrative films and 12 documentaries competing for $100,000 in cash prizes.
Cameron Diaz, Eddie Murphy and Antonio Banderas are set to attend Wednesday's world premiere of Shrek Forever After, which kicks off the festival. Also expected at the weeklong festival are Renee Zellweger, Colin Farrell, Kirsten Dunst, James Franco and Amanda Seyfriend.
Robert De Niro and producer Jane Rosenthal founded the Tribeca Film Festival in 2001 to help revitalize the lower Manhattan neighborhood after 9/11. They shared their favorite New York films with PEOPLE.
"Mine's Sweet Smell of Success," De Niro, 66, tells PEOPLE of the 1957 drama with Tony Curtis and Burt Lancaster, about a desperate press agent (Curtis) and a ruthless newspaper columnist. "It's just a terrific movie and a classic New York film. It made an impression. Another movie that I saw when I was a kid and enjoyed was [the 1956 musical biopic] The Eddy Duchin Story, with Tyrone Power. It showed Tavern on the Green with that romantic side of New York."
Rosenthal said her ultimate favorite is Audrey Hepburn in Breakfast at Tiffany's. "It was so iconic," she said. "When I was a kid it made me want to come to New York. I always wanted to be a part of New York."