It was number one within 10 hours of being released, overtaking last week’s official UK number one Gangnam Style.
The full single was released at 00:07 BST, after a 90 second clip was apparently leaked online this week.
The 23rd James Bond film, Skyfall – Daniel Craig’s third outing as 007 – is released in UK cinemas on 26 October.
Adele ended months of speculation over her involvement on Monday, when she posted a picture on Twitter, featuring the cover page of the sheet music for the Skyfall theme, bearing her name alongside that of longtime producer and co-writer Paul Epworth.
The “dark and moody” theme was intended to echo the narrative of the film.
Skyfall was recorded at Abbey Road Studios in London, and features a 77-piece orchestra.
Adele broke her silence on the track in an official message on the James Bond website on Monday: “When we recorded the strings, it was one of the proudest moments of my life.
“I’ll be back-combing my hair when I’m 60, telling people I was a Bond girl back in the day, I’m sure!”
Adele admitted she was a “little hesitant” about accepting the challenge because of the “instant spotlight and pressure” that came with a Bond song.
But, she said it ended up being a “no-brainer” after she fell in love with the script.
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