P.S. Some of these may not be obvious villains, and may be closer to antiheroes. Some were listed on AFI's 100 Years...100 Heroes and Villains list. Also, some may not be obviously "out of character", so for the sake of this post, I will interpret "out of character" as synonymous with "not looking like they want to kill someone." Some of these photos could also have been added to my previous pictorial post.
Robert Englund with Heather Langenkamp, Jsu Garcia, Amanda Wyss and Johnny Depp on the set of A Nightmare on Elm Street (1984)
Nick Castle giving Michael Myers a sip of Dr Pepper on the set of Halloween (1978).
Anthony Hopkins pretending to take a bite out of director Jonathan Demme on the set of The Silence of the Lambs (1991)
Anthony Perkins and Janet Leigh receive a visit from Steve McQueen on the set of Psycho (1960). In the film, Perkins murders Leigh in the shower.
Linda Blair with director William Friedkin on the set of The Exorcist (1973). Technically, the villain is the demon Pazuzu, which of course possesses the body of Regan (Blair).
Malcolm McDowell chatting to a caffeinated Stanley Kubrick on the set of A Clockwork Orange (1971)
Jack Nicholson reading the newspaper alongside co-star Philip Stone on the set of The Shining (1980)
Robert De Niro with director Martin Scorsese on the set of Taxi Driver (1976)
Robert Walker with director Alfred Hitchcock and co-star Farley Granger on the set of Strangers on a Train (1951)
Skeet Ulrich and Neve Campbell take instructions from director Wes Craven on the set of Scream (1996)
Rutger Hauer posing with Sean Young on the set of Blade Runner (1982). Young took a series of polaroid pictures on the set, available here.
Brad Pitt, Edward Norton and director David Fincher grabbing their crotches on the set of Fight Club (1999)
John Cassavetes lounging around on the set of Rosemary's Baby (1968). Am I being too lenient with the term 'villain'?
Jennifer Jason Leigh and Bridget Fonda looking sexy together on the set of Single White Female (1992)
Rutger Hauer taking instructions from director Robert Harmon, and looking uncharacteristically fatigued on the set of The Hitcher (1986)
Tobin Bell with writer/actor Leigh Whannell and actor Michael Emerson on the set of Saw (2004)
Heath Ledger on the set of The Dark Knight (2008)
Marlon Brando on the set of Apocalypse Now (1979)
Louise Fletcher with director Milos Forman on the set of One Flew Over the Cuckoo's Nest (1975)
Barbara Stanwyck receiving a visit from husband Robert Taylor on the set of Double Indemnity (1944)