Francesca Schiavone led from the front as defending champions Italy beat France 3-2 in the Fed Cup semi-finals.
Schiavone played a part in all three victorious rubbers
They will meet Russia, who came from behind to beat the USA by the same margin, in September's final.
Schiavone, who beat Amelie Mauresmo on Saturday, rallied from 5-2 down in the third set to beat Tatiana Golovin 6-4 2-6 7-5 in the second reverse singles.
She then teamed with Roberta Vinci to defeat Nathalie Dechy and Severine Bremond 4-6 6-1 6-2 in doubles.
"They're champions. They showed a lot of character over two hot days," Italy captain Corrado Barazzutti said.
"The conditions were very tough but the girls played with a lot of heart."
It's good to know that I gave 100%, but it's bad to know it wasn't enough this time
Earlier, Mauresmo rallied through oppressive 44C heat to beat Mara Santangelo 6-7 6-0 6-4.
Russia pair Nadia Petrova and Elena Vesnina beat Venus Williams and Lisa Raymond in doubles to clinch their victory in Stowe, Vermont.
After Williams defeated Anna Chakvetadze 6-1 6-4 in the Sunday's opening singles match, Petrova had saved Russia from elimination by beating Meilen Tu 6-1 6-2.
US captain Zina Garrison decided to call on Williams instead of Vania King to join top-ranked doubles player Raymond.
And the match went to a tiebreaker in the second set, the visitors winning 7-5 7-6 (7/1).
"I'm really disappointed because I tried really hard and I really wanted to win," said Wimbledon champion Williams.
"That's why I was here. It's good to know that I gave 100%, but it's bad to know it wasn't enough this time."
US captain Zina Garrison paid tribute to Williams.
"I'm extremely proud," Garrison said.
"First let's talk about Venus. I mean, coming off of Wimbledon, coming here, stuck in the airport for hours and hours and hours.
"Then getting here, very excited to be here, wanted to do whatever it took, wins two matches, then having to play the doubles.
"They (Williams and Raymond) just came up a little short. It really shows the heart of both of them and the rest of the team, as well."