Former world No. 1 star Serena Williams will lead the United States against host Ukraine in a Fed Cup playoff next week.

The best-of-five tie will be staged on red clay at Superior Golf & Spa Resort in Kharkiv on April 21-22.

The 13-time Grand Slam singles titlist Williams will be joined on captain Mary Joe Fernandez' squad by 19-year-olds Christina McHale and Sloane Stephens, and 35-year-old world No. 1 doubles player Liezel Huber. Venus Williams opted against playing next week.

Serena was last year's U.S. Open runner-up and is fresh off her title in Charleston last week.

Team Ukraine is comprised of Lesia Tsurenko, Elina Svitolina, Lyudmyla Kichenok and Nadiya Kichenok. Tsurenko is the highest-ranked Ukrainian, at No. 110 in the world.

The matchup will mark the first-ever meeting between the 17-time Fed Cup champion U.S. and Ukraine. The winner will advance to the 2013 World Group and have a chance to compete for the Fed Cup title next year. The loser will be relegated to World Group II in 2013.

"I know the team and I are very eager for the task ahead of us against Ukraine. This is our opportunity to play for our spot back into the World Group for next year," Fernandez said. "Playing on the road always presents a difficult challenge, but our team has been playing very well lately and will be ready to compete."