The montage of clips include memorable scenes from 'Titanic', 'Four Weddings and a Funeral', 'Romeo+Juliet', 'Ghost', 'Breakfast At Tiffany's' and 'An Officer And A Gentleman'.
The ad does not feature any price promotions, as part of an attempt to build HMV's brand in the face of stiff competition from the internet.
The 60-second ad is accompanied by 'Kissing You', the theme from Leonardo Di Caprio movie 'Romeo+Juliet'. It ends with the line "The films you love for the one you love" and HMV's new strapline "Get closer".
HMV has also developed Valentine's-specific branding, using the motif of a heart-shaped balloon, while the letter "V" in HMV has been replaced with a heart.
The ad will show this weekend across ITV, Channel 4, Five and Sky channels.
Graham Sim, HMV marketing director, said: "Valentine's Day is, clearly, becoming an increasingly important 'gifting' event within the trading calendar, which is reflected by the fact this is our largest-ever campaign.
"However, we believe that only by working closely with our supplier partners to create engaging advertising and compelling product offers can we expect to maximise consumer interest, and the commercial opportunity this presents."
You can view the ad .
HMV launched its new brand campaign last Christmas based on the theme 'The films you love for the people you love'.
It featured scenes from nine Christmas movies but did not include any price promotions, unlike previous HMV Christmas ad campaigns which focused on the retailer's commercial proposition.