The victory gave the Italians an insurmountable 3-0 lead in the best-of-five series, and they went on to win two more matches for a 5-0 shutout.
The 15th-ranked Pennetta opened the series with a win over Lucie Hradecka.
Russia is playing the United States in the other semifinal.
Italy won the Fed Cup in 2006 and 2009.
Kvitova double-faulted to hand Pennetta the first-set tiebreaker, and Pennetta closed out the match with an ace on her first match point before an enthusiastic crowd at the Foro Italico.
Sara Errani then beat Hradecka 6-4, 6-2 and Errani and Schiavone teamed in doubles to defeat Hradecka and Kveta Peschke 6-2, 6-4.