The duo's 1987 version of the Elvis Presley 1972 hit single has topped a BBC Music Vote to be named the top cover version of all time, beating Johnny Cash's cover of Nine Inch Nails' 'Hurt' and The Stranglers' take on Dionne Warwick's 'Walk On By' into second and third place respectively.
BBC Radio 2 and 6 Music's head of music Jeff Smith said: "The Pet Shop Boys have an enviable catalogue of hits and there have been lots of great versions of this classic song.
"Whittling down the long list for the vote was tough but it's great to see that this track still resonates with people today."
The top five was rounded out by Jimi Hendrix's version of Bob Dylan's 'All Along the Watchtower' and Jeff Buckley's cover of 'Hallelujah', which was originally recorded by Leonard Cohen.
The public voted for their favourite track from a top 50 compiled by BBC producers and DJs including Simon Mayo, Steve Lamacq, Fearne Cotton and Trevor Nelson.
BBC Music's Top 10 Cover Versions of All Time:
1. Pet Shop Boys - 'Always On My Mind'
2. Johnny Cash - 'Hurt'
3. The Stranglers - 'Walk On By'
4. Jimi Hendrix - 'All Along The Watchtower'
5. Jeff Buckley - 'Hallelujah'
6. Soft Cell - 'Tainted Love'
7. Joe Cocker - 'With A Little Help From My Friends'
8. Sinead O'Connor - 'Nothing Compares 2 U'
9. Muse - 'Feeling Good'
10. Whitney Houston - 'I Will Always Love You'
Tagged in Elvis Presley Johnny Cash