Angelina claimed the prestigious title because of her "pneumatic figure, feline eyes and lips that could have been stung by several hives of bees".
She narrowly beat Natalie Portman, who finished in second position after "making baldness sexy" in 'V for Vendetta' and setting men's pulses racing with her raunchy pole dancing scene in 'Closer'.
James Bond actor Daniel Craig - who wowed women in 'Casino Royale' when he emerged from the ocean in a pair of tight-fitting blue swimming trunks - came third, while 'Fantastic Four' beauty Jessica Alba finished fourth.
'Pirates of the Caribbean' star Johnny Depp rounded off the top five.
Other entries on the list, which was voted for by 20,000 film fans, included Matt Damon - who was recently voted People magazine's Sexiest Man Alive for 2007 - who took 17th spot.
British stars Christian Bale, Kate Winslet, Orlando Bloom, Kate Beckinsale and Clive Owen all made it in to the top 25, with 'Harry Potter' actor Daniel Radcliffe coming in at 23.
'Volver' actress Penelope Cruz took 50th position and the entire list was rounded off by 'Die Hard 4.0' actress Mary Elizabeth Winstead.

Empire magazine's 100 Sexiest Movie Stars Ever top ten:

1. Angelina Jolie
2. Natalie Portman
3. Daniel Craig
4. Jessica Alba
5. Johnny Depp
6. Eva Green
7. Brad Pitt
8. Scarlett Johansson
9. Keira Knightley
10. Gerard Butler