Europe's captain Alison Nicholas named Scot Janice Moodie, Wales' Becky Brewerton and Swede Anna Nordqvist as wildcards to make up her 12-strong tream.
Third seed Lleyton Hewitt was beaten 7-6 (7-1) 6-4 by Frenchman Arnaud Clement, who now meets Marat Safin after the Russian beat Wesley Moodie 7-6 (7-5) 7-6 (11-9).