Smith is the first British solo male vocalist to sing over the opening credits since Tom Jones in 1965.
The 23-year-old artiste has co-written the track with fellow Grammy-winner Jimmy Napes.
The song, whose full version runs for four minutes and 38 seconds, begins with the words: "I've been here before / But always hit the floor."
"I've spent a lifetime running, and I always get away. But with you I'm feeling something, that makes we want to stay," it continues.
"Ladies & Gentleman, here it is... The James Bond 2015 theme tune to #Spectre 'Writing's On The Wall' http://po.St/WOTWsp," he tweeted while giving the link to the track.
The singer said he had waited for long for this moment. "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," he wrote.
The song bagged mixed response from the music lovers.
Former Bond actor Roger Moore called "Writing's On the Wall" "very haunting and wonderfully orchestrated".
Other Twitter users were less complimentary, with one describing it as the "worst Bond theme ever".
Comedian David Schneider tweeted, "The name is Bland. James Bland. #writingsonthewall #SamSmith"
A fan wrote, "Says he wrote it in 20 minutes. Perhaps he should have spent longer."
The song's title appears to derive from a scene in Spectre, viewed briefly in the film's trailer, in which Bond's name is found scrawled upon a wall.
"Spectre", which will feature Daniel Craig in his fourth performance as James Bond, is due to be released in the UK simultaneously with its London world premiere on October 26 before hitting the US on November 6 n India on November 20.
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