The 44-year-old Williams, a 23-time Grand Slam winner, has not competed since the 2022 US Open. The American and Mboko, 19, received a wildcard for the doubles draw at Queen's Club.
"The Queen is back. An honour to share the court with one of the greatest athletes of all time this week," Mboko, who had hinted about Williams' return after winning her French Open second-round match, said in a post on Instagram.
"Even more excited to play doubles together! Tennis is pretty special."
Williams announced her return on social media after speculation intensified following her re-entry into the anti-doping testing pool last year, despite previously saying she was "evolving away from tennis".
Williams will take the court in London at the WTA 500 tournament running from June 8th to 14th.
She has won 14 Grand Slam doubles titles alongside her sister Venus, and the pair remain undefeated in major finals.
Mboko, who is ranked ninth in singles, also claimed Williams as her "idol" at Roland Garros last week.