The best-of-five tie will be staged on an indoor hardcourt at Worcester's DCU Center.
The 22-year-old Azarenka is fresh off her first-ever Grand Slam title, which she attained by beating former top-ranked star Maria Sharapova in last week's Aussie Open finale. The Belarusian slugger also ascended to No. 1 in the world in the process.
Sunday's reverse singles in Massachusetts will pit the U.S. Open runner-up Williams against Azarenka and the New Jersey native McHale versus Govortsova, while the doubles currently call for an American duo of Venus Williams and Liezel Huber to battle a Belarusian pairing of Azarenka and Govortsova on Day 2.
Venus hasn't played anywhere since pulling out in the first week of last year's U.S. Open, as she has been slowed by Sjogren's syndrome, an incurable autoimmune disease that causes fatigue and joint pain.
The former No. 1 Serena is a 13-time Grand Slam champion, while her fellow former top-ranked older sister boasts seven major championships.
The Americans, captained by Mary Joe Fernandez, and Belarusians are not in the World Group this year, which means neither team can capture the Fed Cup title in 2012. The U.S. is the all-time leader with 17 championships.
This will mark the first-ever Fed Cup meeting between the U.S. and Belarus.
The winner here will advance to the World Group playoffs and have a chance to compete for the Fed Cup title next year.