The QR codes will allow customers to buy 20th Century Fox Blu-ray discs and DVDs, such as 'Rise of the Planet of the Apes' via the HMV mobile app.
Consumers will be able to scan the code for a title that appeals to them on posters at bus shelters.
This will automatically launch hmv.com on the appropriate product page and the purchase can be made through the app.
Mark Hodgkinson, the new marketing and ecommerce director at HMV, said the initiative comes as the retailer looks to allow its customers to "discover and consume entertainment content in the way that best suits them".
Twentieth Century Fox Home Entertainment managing director Robert Price said the mobile technology is designed to provide time-stretched consumers with "new distribution points".
The outdoor campaign will run in London, Manchester, Leeds, Nottingham, Bristol, Glasgow and Edinburgh.
Fox titles included in the initiative include 'Rise of the Planet of the Apes', 'X-Men First Class' and 'Alien Anthology'.
Creative was handled by The Entertainment Agency and Posterscope handled the media planning and buying.
News of the innovation coincides with HMV also trialling its first ever store dedicated to technology, which is located in the One New Change shopping centre in the City of London.
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