The Czech Republic, seeking a third consecutive title, lost 3-1 in Palermo as Roberta Vinci clinched the decisive pointwith a 6-3 6-7 (2-7) 6-3 win over Lucie Safarova.
Federer had only just flown back to Europe following his five-set defeat by Juan Martin Del Potro in Monday's US Open final, but beat Simone Bolelli on Friday and then secured the decisive third pointwith a 6-3 6-0 6-4 win over Potito Starace on Sunday.