Seles will lead the top-seeded Americans against Austria in one of eight confrontations around the world.
Second seed Belgium begins defense of its title in the world's premier international women's team tennis event against Australia in Brussels at the Royal Leopold Club.
The key change to the 2002 competition is the return to a 16-nation World Group, which provides increased opportunites for nations to host ties in the first two rounds. The first-round winners will meet in the quarterfinals on July 20-21 and the semifinals and final are slated for the week of Nov. 4.
The United States won the 1999 and 2000 Fed Cups before pulling out of last year's final, citing security worries after the terrorist attacks of Sept. 11.
Seles, the world No. 6, faces Barbara Schwartz in the opening singles match on the clay courts of the Olde Providence Racquet Club. The former world No. 1 will be competing in her first Fed Cup match since November 2000, when she defeated Conchita Martinez en route to the Americans' 5-0 whitewash of Spain in the final at Las Vegas.
"You're not playing as an individual, you're playing for your country," Seles said. "I really have some great memories of the past Fed Cup ties that we've played. It's just a very different atmosphere. The crowd is a lot more into it."
Jennifer Capriati, the current world No. 2 and reigning Australian Open champion, last competed in the Fed Cup in November 2000. The 26-year-old, who owns a 10-3 mark in Fed Cup play, meets Evelyn Fauth in the second singles match.
The Americans have won the event a record 17 times. With the United States out of the way last year, Belgium won its first Fed Cup behind the play of French Open finalist Kim Clijsters and Wimbledon runner-up Justine Henin.
Spain, meanwhile, hosts Hungary at Almeria. Arantxa Sanchez-Vicario, who will be playing in her 55th Fed Cup tie, meets Rita Kuti Kis following the match between Spain's Angeles Montolio and Hungary's Zsofia Gubacsi.
France's Amelie Mauresmo and Sadrine Testud travel to Argentina to take on Mariana Diaz-Oliva and Paola Suarez on the clay courts of the Buenos Aires Lawn Tennis Club in the opening singles matches.
Mauresmo has recorded wins in six of her last seven Fed Cup singles matches.
In the other first-round ties, Croatia hosts the Czech Republic, Russia visits Germany, the Slovak Republic takes on Switzerland, and Italy meets Sweden.
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UPI Sports Results for September 20, 2014