With all the fantasy film craze, how about NWN2 as a movie? ;)

Say who you'd like to play who or improve on my list:

Khelgar - Tony Curran, moderately deep scottish accent, and a voice that I could associate with a "I love to fight" character. ;)
Neeshka - Brittany Murphy
Elanee - Jessica Biel
Qara - Joss Stone, after seeing her cameo in Eragon I think this could work
Shandra - Ali Larter
Sand - Val Kilmer, I think he could convey Sand's smug and condescending personality
Grobnar - Warwick Davis
Casavir - Hugh Jackman
Bishop - Josh Duhamel
Zhjaeve - Carrie Ann Moss, can convey that ultra-serious intensity from The Matrix
Ammon Jerro - Patrick Stewart

NPCs:

Aldanon - I'm stuck here
Sir Nevalle - Heath Ledger
Lord Nasher - Derek Jacobi
Officer Kana - Rosamund Pike

For villains:

Black Garius - John Malkovich
Lorne - Nathan Jones
Torio Claven - Eva Green, I think she can definitely turn up the nastiness for this role
Sydney Natale - Judi Dench?

Nah, Neeska should be Ellen DeGeneres, Brittany's nowhere near mischievous enough :D
Aldanon should be played by Ian McKellan, and Sir Nevalle should be Colin Firth

Peronally, I'd play the PC ;)