The singer has recorded Writing's On The Wall for new movie Spectre.
He follows in the footsteps of stars including Shirley Bassey, Madonna and Adele, who have all previously recorded Bond themes.
The song debuted on Friday (25Sep15) to mixed reviews, with some fans praising its "haunting" qualities while others branded it the "worst Bond theme ever." One scathing reviewer wrote, "Great cover of 'Earth Song', mate. When's the new Bond theme out?"
However, Sam's track has won the favour of former Bond star Roger.
In a post on Twitter.com, he writes, "@samsmithworld has delivered a very haunting and wonderfully orchestrated #spectre theme song. Well done!"
After the track was unveiled, 'Bond' became a trending topic on Twitter.com along with Shirley Bassey, who sang three Bond tunes.
Sam has become the first British male solo artist to tackle a Bond theme since 1965, when Tom Jones released Thunderball.
After Writing's On The Wall's debut, Sam tweeted, "I have been dreaming of this moment for a long long time... Thank you for all your amazing messages. Today is such a special day for me and I am so grateful to everyone supporting this track."
Adele was the last artist to record a Bond theme and she scored a huge hit with 2012's Skyfall. She won an Oscar for her hard work, as well as a BRIT Award.
Spectre hits cinemas in Britain on 26 October (15), 12 days before the film opens in the U.S. on 6 November (15).
It marks Daniel Craig's fourth outing as the suave spy and he is rumoured to be stepping down after its release.
Fellow Brit Idris Elba has been hotly tipped as his replacement.