Williams, who earlier this week declared her intention to retire after the upcoming US Open, will open her tournament on Tuesday (AEST) against the 19-year-old Briton, who is currently ranked No.10 in the world.
The 23-time grand slam champion recorded her first singles win in more than a year at this week's Canadian Open, defeating Nuria Parrizas-Diaz on Tuesday (AEST), before losing in the second round to Belinda Bencic.
In between the matches, Williams had signaled her retirement plans in an article in Vogue magazine.
The first-round clash is one of several intriguing matches including No.14 seed Karolina Pliskova meeting Venus Williams, two-time Major winner Victoria Azarenka facing Estonian veteran Kaia Kanepi.
In-form Simona Halep is drawn against 2021 Australian Open semi-finalist Karolina Muchova, while four-time grand slam winner Naomi Osaka will face Zhang Shuai.
In the men's singles draw, No.12 seed Matteo Berrettini will face Frances Tiafoe straight up, while Australia's Nick Kyrgios is scheduled to take on Alejandro Davidovich Fokina.