Pennetta won both her singles matches in the tie
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Italy will face Belgium in the Fed Cup final after both nations came through their semi-final ties on Sunday.
The Italians reached their first final with a 3-1 victory over Spain in Zaragoza, with Flavia Pennetta securing the winning point.
And 2001 champions Belgium joined them after Kim Clijsters hammered Vania King, 17, 6-0 6-1 to put the home side 3-0 up against the USA in Ostend.
The Fed Cup final will take place in Belgium on 16-17 September.
"We had an ideal start on Saturday and now I was able to finish it off," said Clijsters. "And I played a lot better."
Kirsten Flipkens and Mashona Washington were locked at 2-6 3-1 in the dead fourth rubber when the American retired with a strained ligament in her right knee, putting Belgium 4-0 up.
With Italy leading 2-0 overnight, Anabel Medina Garrigues gave Spain hope with a 6-2 6-2 win over Francesca Schiavone in the third rubber.
But Pennetta ended Spanish hopes in Zaragoza when she beat Lourdes Dominguez 6-2 6-4.
"This is unbelievable because, in the beginning, we didn't think we could make it to the final," said Pennetta.
"It's an incredible sensation to win the last point."
The doubles match between Spain's Virginia Ruano Pascual and Maria Antonia Sanchez against Romina Oprandi and Mara Santangelo was cancelled due to extreme heat.