The British rockers celebrated a double victory as they were awarded Best Live Band and Best Music Film for 'Crossfire Hurricane' and member Ronnie Wood, who attended the ceremony with his new wife Sally, admitted he was thrilled with the honours.
The 65-year-old star told the audience: ''Thank you. Mick, Keith and Charlie were too nervous to come out from backstage so I stepped up. About time I think and thanks very much, this is a good award show this.''
Florence Welch of Florence And The Machine also received two awards, taking home the prestigious Best Solo Artist for the second year in a row and Best Dance-floor Anthem for her collaboration with Calvin Harris 'Sweet Nothing'.
The 26-year-old singer told fans she was shocked to win, saying: ''Well thank you very much. This is so wonderful; I didn't expect to get this again. I'd just like to thank everyone in my band and NME and have a great night.''
Rockers Biffy Clyro opened the show with a performance of 'The Captain' and 'Victory Over The Sun' before picking up the coveted award for Best British Band, beating off tough competition from a number of groups including The Cribs, who performed 'Mirror Kisses' and were later awarded the Teenage Cancer Trust Outstanding Contribution to Music.
The Killers won Best International Band and frontman Brandon Flowers claimed it was an extra special victory.
He said: ''In Las Vegas where we come from you can't just pick up an NME so it means something to us this award, and we're grateful, so thanks.''
The event, which also featured performances from Paul Weller and Miles Kane, was hosted by comedian Russell Kane and over 10 million votes were cast by the magazine's readers.
The Maccabees picked up Best Album for the critically-acclaimed 'Given to The Wild', and the Foals performed their hit single 'Inhaler', which was awarded Best Track.
The Smiths guitarist Johnny Marr was awarded the title of Godlike Genius, presented to him by Ronnie Wood and he told the crowd: ''I think it's serious and funny and sweet and very rocking to get the Godlike Genius Award. I'm looking forward to being lazy for the rest of my life.''
Blur picked up the Best Reissue award for '21', surprising Graham Coxon, who said: ''Reissues, flippin' heck, still getting away with it. This was a box set that was in my cupboard for about 20 years but it was on cassette and the box was a shoe box!''
The Artic Monkeys 'R U Mine' won the award for Best Music Video.
But it was a disappointing night for One Direction as the boy band was awarded Worst Band and member Harry Styles was named Villain of the Year.
FULL LIST OF WINNERS:
TEENAGE CANCER TRUST OUTSTANDING CONTRIBUTION AWARD
BEST BRITISH BAND supported by SONOS
BEST ALBUM supported by Hoxton Gin
'Given To The Wild' The Maccabees
BEST INTERNATIONAL BAND supported by Rekorderlig Cider
BEST TRACK supported by Blackstar Amps
BEST TV SHOW
BEST MUSIC FILM
The Rolling Stones: 'Crossfire Hurricane'
BEST SOLO ARTIST
BEST NEW BAND supported by Spotify
BEST MUSIC VIDEO
'R U Mine?' Arctic Monkeys
BEST FESTIVAL supported by Farah Vintage
Reading & Leeds Festivals
BEST LIVE BAND
The Rolling Stones
BEST DANCEFLOOR ANTHEM
'Sweet Nothing' Calvin Harris featuring Florence Welch
PHILIP HALL RADAR AWARD
Child Of Lov
Alana Haim, Haim (@babyhaim)
Mike Skinner: 'The Story Of The Streets'
MUSIC MOMENT OF THE YEAR
Olympics opening ceremony
HERO OF THE YEAR
VILLAIN OF THE YEAR
BEST SMALL FESTIVAL
BEST FAN COMMUNITY
'The Hobbit: An Unexpected Journey'