The singer will be joined by Russian soprano Aida Garifullina as the pair take to the stage 30 minutes before Russia and Saudi Arabia kick off the tournament.
"I'm so happy and excited to be going back to Russia for such a unique performance," Williams told The Mirror.
"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."
Garifullina added: "I never imagined I would be part of this huge celebration, the World Cup, happening in my own country. The image that I will be presenting to the whole world will be very symbolic and associated with a dream coming to life."
Russia vs. Saudi Arabia, which kicks off at 4pm BST, is the only game taking place on Thursday.