74. Elizabeth Hurley, the devil in Bedazzled (2000).
73. Sting, Feyd-Rautha Harkonnen in Dune.
72. Bruce Payne, Charles Rane in Passenger 57.
71. Jonathan Hyde, Van Pelt in Jumanji.
70. Ray Winston, George McHale in Indiana Jones and the Kingdom of the Crystal Skull.
69. Sean Connery, Sir August de Wynter in The Avengers.
68. Alfred Molina, Dr. Octopus in Spiderman 2.
67. Cary Elwes, Ella Enchanted and Twister.
To be fair, Cary Elwes may not have made the most effective villain, but he made an EXCELLENT farm boy in The Princess Bride.
(Lest we forget)
Sigh. Anyway, where were we?
66. Art Malik, Salim Abu Aziz in True Lies.
65. Peter Cook, the devil in Bedazzled (1967).
64. Roger Allam, V in V for Vendetta.
63. Tom Hollander, Lord Cutler Beckett in Pirates of the Caribbean: Dead Man's Chest, At World's End.
62. Sean Pertwee, Detective Virgil Kane in The 51st State.
61. John Hurt, Percival Graves in King Ralph.
60. Tim Curry in IT and Legend.
59. Richard O'Brien, Riff Raff in The Rocky Horror Picture Show.
58. Robert Carlye, Renard in The World is Not Enough.
57. Timothy Dalton, Neville Sinclair in The Rocketeer.
56. David Suchet, Nagi Hassan in Executive Decision.
55. David Warner, Edward Dillinger/Sark in Tron.
54. Sean Bean in Goldeneye and National Treasure.
Winter is coming :(
53. Doug Bradley, Pinhead in Hellraiser.
52. Mark Strong in Sherlock Holmes and Kick-Ass.
51. Tom Wilkinson, Thomas Griffin/Juntao in Rush Hour.
50. Richard Attenborough in Brighton Rock and Jurassic Park.
49. Ray Milland, Tony Wendice in Dial M for Murder.
48. Pam Ferris in Matilda and Harry Potter and the Prisoner of Azkaban.
47. Patrick Stewart, Dr. Jonas in Conspiracy Theory.
46. Joss Ackland, Lethal Weapon 2 and Bill and Ted's Bogus Journey.
45. Timothy Spall, Peter Pettigrew in the Harry Potter series.
44. Dougray Scott, Sean Ambrose in Mission Impossible II.
43. Charles Dance, Benedict in Last Action Hero.
42. Michael Sheen, Aro in the Twilight saga.
41. Paul Bettany, Silas in The Da Vinci Code.
40. David Tennant, Barty Crouch in Harry Potter and the Goblet of Fire.
39. Christopher Eccleston in Gone in Sixty Seconds, Thor: The Dark World, and GI Joe.
38. Peter Cushing in the Star Wars series.
37. David Bowie in Labyrinth and The Last Temptation of Christ.
36. Steven Berkoff, in Beverly Hills Cop, The Tourist, Rambo: First Blood Part II, and Octopussy.
35. Bill Nighy, Viktor in Underworld.
34. Brendan Gleeson, Harry Potter and the Goblet of Fire.
33. Billie Whitelaw, Mrs Baylock in The Omen.
32. Brian Cox, Agamemnon in Troy.
31. Tim Roth in Rob Roy, The Incredible Hulk, and Planet of the Apes.
30. Iain McDiarmid, Emperor Palpatine/Darth Sidious in the Star Wars series.
29. Tom Hardy in The Dark Knight Rises and Star Trek: Nemesis.
28. David Prowse, Darth Vader in Star Wars IV: A New Hope, V: The Empire Strikes Back, and VI: Return of the Jedi.
Of course, David Prowse (also the Green Cross Code man in the UK) was just Vader's body. James Earl Jones provided the voice.