Fed Cup holders Italy overcame two stern tests on Sunday to beat Ukraine 4-1 in Kharkiv and book their place in the semi-finals where they will play the Czech Republic.
Russia will play the United States in the other semi-final.
Former world number one Ana Ivanovic's poor form continued from Saturday as she lost her singles and doubles matches to hand Russia a 3-2 triumph over Serbia in Belgrade.
The Czechs squeezed past Germany 3-2 while the US overcame France 4-1.
Going into the second day in Ukraine tied 1-1, Italian Flavia Pennetta edged a tight match with Alona Bondarenko 7-5 7-6, handing Francesca Schiavone the chance to seal the tie which she duly took with an impressive comeback victory against Kateryna Bondarenko, eventually winning 2-6, 6-1, 6-1.
"I played much better under pressure and I was fighting from the beginning to the end even if I did not always reach my best," world number 12 Pennetta told the Fed Cup website (www.fedcup.com).
Ivanovic, by contrast, was unable to find any of the swagger that took her to French Open success in 2008 as she subsided all too easily in front of her own fans, registering just five games in both her singles loss to Alisa Kleybanova and, partnering Jelena Jankovic, in the doubles against Kleybanova and Svetlana Kuznetsova.
While Ivanovic is struggling for form, American Melanie Oudin is growing ever more confident and led from the front in the northern French town of Lievin.
After helping set up a 2-0 lead on Saturday, the 18-year-old 2009 US Open quarter-finalist got the better of Julie Coin 7-6, 6-4 to give her country an unassailable lead.
"I was a bit nervous and she was serving great, but as the match advanced I got more and more confident and I'm obviously thrilled that I was able to allow the US to go to the semis," Oudin said.
Unlike the French, the Czech Republic made full use of home advantage in Brno to beat Germany 3-2 with doubles pair Lucie Hradecka and Kveta Peschke beating German duo Anna-Lena Groenefeld and Tatjana Malek 6-1, 6-3 in the deciding rubber.
The semi-finals will be contested from April 24-25.