HMV has agreed deals with all the major Hollywood studios - Sony Pictures, Twentieth Century Fox, Walt Disney and Warner Bros - through its tie-up with FilmFlex, the VOD rental joint venture between Sony and Disney.
The retailer has also secured agreements with a raft of independent studios and more than 30 distributors, including Entertainment One and Momentum Pictures.
HMVon-demand will use FilmFlex's white-label movie services to offer new releases to rent online via transactional video on-demand (TVOD) after their theatrical and DVD release, but before the pay-TV window when they are typically shown on Sky Movies. The company said that many films would be available on the same day as their DVD release date.
New release movies available to rent now on HMVon-demand include Cars 2, Zookeeper, Rio, X-Men: First Class and Bad Teacher.
On November 28, the service will start offering Horrible Bosses, followed by Harry Potter and the Deathly Hallows: Part 2 on December 5, and The Hangover Part II on December 12.
HMV has endured a torrid year so far, as tough operating conditions and a 10% slump in sales caused the firm to close down around 60 of its high street stores.
However, the retailer has been looking to expand its digital business and leverage its recognised consumer brand with online entertainment services, including HMVon-demand.
Rentals will initially be just available over the internet to PCs and laptops to watch on or offline, but HMV intends to expand to other platforms in the future, potentially including smartphone, tablets and connected TVs.
"We're excited to be working with FilmFlex to launch HMVon-demand and offer our loyal and significant customer base a best-in-class movies-on-demand service," said HMV marketing & e-commerce director Mark Hodgkinson.
"As an entertainment brand built on specialist choice our remit has always been to enable people to discover and enjoy content however and whenever they want.
"With a growing number of consumers now incorporating video-on-demand into their viewing and purchasing habits, the time is right to include a digital service into our own offer. Partnering with FilmFlex will allow us to extend our brand into new areas and deepen the relationship with our customers."
HMVon-demand will initially go into a "soft launch" through the HMV online store and by engaging the two million members of the PureHMV rewards scheme.
The company intends to ramp up the marketing activity in January 2012 with a multi-platform marketing campaign, when it will compete with the subscription movies streaming offerings of the Amazon-owned LoveFilm and the incoming US media giant Netflix.
FilmFlex will manage all digital rights and security on behalf of HMV, after the firm built the online HMVon-demand platform, including billing, customer service and on-site promotion.
Jeff Henry, the chief executive of FilmFlex, said: "Our deal with HMV illustrates perfectly the benefit of combining their well-known brand and high traffic volumes with our own expertise in technology and content.
"This partnership is another indication why FilmFlex is the best movies-on-demand white-label service for any major media, retail or publishing brand in the UK who wants to monetise their traffic.
"Our future potential to offer other content, as well as movies, means we are uniquely positioned to offer new and existing clients the best VOD service in the marketplace."
FilmFlex powers the on-demand movies service provided by cable TV firm Virgin Media, and the firm also recently started handling download-to-rent options on Film4oD, Film4's on-demand service.