The actress will take on the role of Miss Havisham, who is abandoned at the altar on her wedding day, BBC Films announced.
Jeremy Irvine, who has also committed to Steven Spielberg's Warhorse, will play Pip, the orphan she takes into her home.
The only other name rumoured for the cast is Ralph Fiennes, who is reportedly considering the role of the escaped convict Magwitch.
BBC Films also announced several other projects including adaptations of children's novels Swallows and Amazons and Peter Pan in Scarlet.
Best-selling One Day author David Nicholls will be penning the script.