I know I would buy these in a heartbeat:
Conan the Barbarian (the REAL one not the upcoming remake - regular and/or "camo" version)
Neo from the Matrix
Morpheus from the Matrix and/or Matrix Reloaded (preferably this one, w/samurai sword and all)
Trinity
Agent Smith (hopefully with alternate Agent heads)
Beatrix Kiddo from Kill Bill
Gandalf the White
Gandalf the Grey, Bilbo and Thorin Oakenshield from the upcoming Hobbit movie
JL Picard, Riker (w/beard), Data and Worf from Star Trek: TNG
Chewie
I would likely buy these as well:
John Matrix (from Commando)
... Quite possibly any Schwartzenegger figure from Total Recall, the Running Man, True Lies, Pumping Iron (yes I am an Arnie fan).
Kirk and Spock from either the original series, movies (in red uniforms) or new movies.
Likely any SW figures they end up doing, but quite frankly I don't think we need a new Old Ben, or anyone with armour (Vader, Boba Fett, Stormies/Clones) as Sideshow's doing a bang-up job on most stuff. I wouldn't mind a Hot Toys Luke, Han and Leia though, from the first movie.