The pop star will entertain the crowd before the football tournament’s opening match between Russia and Saudi Arabia on Thursday.
It comes after Williams was forced to deny his 2016 song Party Like A Russian included derogatory references to Russian president Vladimir Putin.
In the track, Williams sings about a leader who “alleviates the cash from a whole entire nation, takes loose change and builds his own space station,” and adds: “Ain’t no refutin’ or disputin’ – I’m a modern Rasputin”, while women dressed as ballerinas dance around him in the music video.
Sergey Knyazev, a member of the National Association of Event Organisers, reportedly told pro-Kremlin news channel Life News at the time: “This will upset those who previously wanted him to perform, who brought him to Moscow, or wanted him to perform at their events abroad.
“None of these people, big corporations or individuals who want him at their event, want to end up as the butt of this joke. It is a joke about ‘new Russians’.”
Following the controversy, Williams told fans on Twitter that the song “is definitely not about Mr Putin”.
The former Take That star will perform at the opening ceremony at Moscow’s Luzhniki Stadium along with Russian soprano Aida Garifullina.
Former Brazil striker Ronaldo will also feature at the event.
Williams said: “I’m so happy and excited to be going back to Russia for such a unique performance.
“I’ve done a lot in my career, and opening the FIFA World Cup to 80,000 football fans in the stadium and many millions all over the world is a boyhood dream.”