The online content subscription service will get instant and exclusive on-demand access to Fox movies in the "second pay television window", essentially after they have been on Sky Movies.
The deal starts with Fox titles released in cinemas in the UK in 2011, which will be offered to LoveFilm streaming subscribers from March 2013.
Alongside the films, the deal also includes a range of television shows for streaming on LoveFilm, starting next month. The content includes motorcycle drama Sons of Anarchy and all seasons of 24, along with Prison Break, Buffy the Vampire Slayer and its spin-off Angel.
LoveFilm has been busy snapping up a range of content deals over the past 12 months as it looks to compete with rival services, particularly US media giant Netflix, which launched in the UK earlier in the year.
The Amazon-owned firm has also agreed recent deals with Warner Bros., Sony Pictures, NBC Universal, Entertainment One, StudioCanal, Disney, ABC, BBC and ITV.
Separately to the streaming deal, LoveFilm will continue to rent Fox titles on DVD and Blu-ray via its rental-by-post business.
"It feels great to announce another major studio deal for LoveFilm. Twentieth Century Fox is one of the world's leading studios, known across the globe for creating fantastic, iconic content," said LoveFilm managing director Jim Buckle.
"This partnership will give LoveFilm members access to the studio's huge range of recent movies and the opportunity to revisit some of the best American TV series produced in recent years."
Fox's Gina Brogi added: "We are delighted to be partnered with LoveFilm on this new window for Fox films in the UK.
"This film and series agreement enables us to give UK fans yet another avenue to enjoy the great stories and characters they have come to know and love from our studio."
Last month, LoveFilm announced the addition of high definition (HD) content on LoveFilm Instant, the streaming-only package launched last year.