Maya Joint of Australia will face the 23-time Grand Slam winner.
Joint is ranked 53rd in the world, and the 20-year-old has never made it past the first round of Wimbledon.
Serena Williams retired in 2022 but recently made a comeback at Queen's. She then received a wildcard into Wimbledon, a tournament she has won seven times.
Williams will also play in the doubles tournament with her 46-year-old sister, Venus.
Wimbledon starts on Monday.
Correction: A previous version gave incorrect information about Maya Joint's world ranking.
