The Canadian had limped off the court in tears on Wednesday, conceding her match against Karolina Pliskova with the scores 6-2 3-4 to the Czech in the second set, leaving her Wimbledon campaign in doubt.
Williams and her partner had breezed to a 7-6 (7-2) 6-2 victory over third-seeded duo Nicole Melichar-Martinez and Erin Routliffe in the former's first appearance since the 2022 US Open.
The pair were scheduled to face Canadian Layla Fernandez and German Laura Siegemund in the second round of the doubles tournament tomorrow, but Mboko's injury means that the match will not take place and their tournament is over.
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The former world No 1, though, has added the Berlin Tennis Open to her comeback schedule, which begins on June 15 live on Sky Sports Tennis, with her doubles partner yet to be confirmed.
"Every tournament I add to my schedule right now feels special, and Berlin is no exception," said the 23-time Grand Slam singles champion on the official Berlin Open website.
"I'm excited to compete in front of the German fans and continue building momentum throughout the grass-court season."
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