Anne Shirley: played by Karen Gillan (you know I had to. MARRY ME KAREN), Anne is a lovely, witty, compassionate, generally awesome college co-ed going for her BA at Redmond College, where she keeps old friends and meets new ones.
Philippa Gordon: played by Emmy Rossum, Phil is the delish upperclass beauty of Bolingbroke and Anne's closest new friend at college. She is at first horrified to find herself falling in love with an ugly minister.
Gilbert Blythe: played by Ryan Gosling, Gilbert is one of Anne's childhood friends from Avonlea, who has been nursing an unrequited love for her since the day she cracked a slate over his head.
Roy Gardner: played by Henry Cavill, Roy is the ultimate ideal of Anne's dreams--or so she thinks.
Miss Patty: played by Helena Bonham Carter, Miss Patty is the eccentric owner of Patty's Place, the gold-standard of a cottage that Anne and Co. rent for their years at Redmond.
Stella Maynard: played by Ellen Page, Stella is one of Anne's friends from Queens College.
Priscilla Grant: played by Laura Vandervoort, Pris is another of Anne's friends from Queens.
Charlie Sloane: played by Lee Ingleby, Charlie is another old friend from Avonlea, also in love with Anne. He has ridiculous ears.
Aunt Jamesina: played by Olympia Dukakis, Stella's Aunt Jimsie lives with the girls at Patty's Place and keeps house for them, and is the coolest aunt ever.
And that's how Diana casts it! All images pulled from Google and Wikipedia.