The multi-year content deal will give LoveFilm subscribers access to a range of titles from June 2012 in the second pay-TV window, essentially after they have aired on Sky Movies.
LoveFilm members will be able to stream the Academy Award-winning Facebook movie The Social Network, Angelina Jolie's action thriller Salt and sci-fi action blockbuster 2012 as part of their existing subscription.
Users will also be able to look forward to the future release of Arthur Christmas, after the animated movie comes into the second pay window.
The deal further brings a range of kids TV content from Sony to LoveFilm, including Transformers, Spectacular Spider-Man and The Karate Kid for streaming on PC, Sony's PS3, the Xbox 360, Apple iPad and connected TV devices.
LoveFilm will continue to rent Sony Pictures titles as usual on DVD and Blu-ray via its postal DVD business.
Simon Calver, the chief executive of LoveFilm, said: "Our latest major content agreement means we'll be able to exclusively offer our members world-class content from Sony Pictures.
"The number of recent high-profile deals we have secured means we are able to keep expanding the service, offering our members high-quality films and TV and the ability to watch as much as they want for one low monthly price."
LoveFilm has been busying agreeing a range of content deals as it prepares for the stiff competition of US streaming giant Netflix launching in the UK and Ireland next year.
Yesterday, Netflix snapped up a raft of BBC television content for its UK service, in addition to already-announced deals with MGM, Lionsgate and Miramax.