The jointly branded DVD rental service will appear on lastminute.com's UK homepage, where customers can click to search the 20,000 DVDs on offer. New subscribers benefit from a four-week free trial offer.
The deal includes joint branding on LOVEFiLM DVD envelopes and ticket wallets issued by lastminute.com. Access to the DVD rental site can be found at http://dvd.lastminute.com.
Paul Shaw, UK head of lifestyle at lastminute.com, said: "This deal fits neatly with our mission to offer a comprehensive service for all our customers' needs. LOVEFiLM suits our customer demographic and brand appeal."
Mark Livingstone, chief executive officer of LOVEFiLM, said: "The new partnership with lastminute.com is a great illustration of two like-minded companies joining forces to create a proposition that truly benefits their respective client bases. Both of us offer a spontaneous service with a feel-good reward at the end of it."
The deal comes as the online DVD rental market continues to hot up. UK players such as Webflix and Video Island are preparing for an invasion from US brands such as Netflix, which is planning to launch a service in the UK in the second half of this year.
High street rental giant Blockbuster launched a revamped DVD rental service of its own in May, while Tesco has struck a partnership with Video Island to offer DVD rentals on Tesco.com.