Kvitova's 10th consecutive win in the team competition put the Czechs 3-0 to the good and clinched a final against either Serbia, who beat Russia 3-2 in their semi-final.
Schiavone, who had been suffering a neck injury during the weekend, showed plenty of grit and looked set to push the world number three to a deciding set.
However, Kvitova came back from 2-4 down in the second set to force a tiebreak against the world number 12 and then cruised through the breaker 7-1.
"The weight was rather on my back today. I'm happy with how I handled it and getting a 10th straight victory," Kvitova said.
Playing at home for the first time in two years, the Czechs never allowed Italy a glimmer of hope as they won all the singles matches in straight sets.
Italy had won the last four meetings between the nations, but with Kvitova in such good form for her country they are now poised retain the trophy they won by beating Russia in last year's final which was their first success since winning it as Czechoslovakia in 1988.
Jankovic's win gave the visitors an insurmountable 3-1 lead against Russia in their semi-final, played on a red clay court laid on top of the ice rink at Moscow's Megasport arena.
"I still cannot believe that we are in the Fed Cup final," an emotional Jankovic told reporters.
"I well remember the times when we were still playing in the lower divisions and were only dreaming of playing for the Fed Cup trophy," said the former world number one.
"I had felt quite a lot of pressure before this match but was able to overcome it and tried to play my game. Svetlana is a great player and is always dangerous on any surface but I just kept my concentration at all times."
Looking ahead to the final Jankovic said: "It's going to be another tough tie. The Czechs have a great team, but I think after today's victory we are capable of beating anyone now."
Two-time grand slam winner Kuznetsova struggled to explain her sub-par performance.
"I'm still trying to figure out what went wrong today," said the former world number two, who has slipped to number 27 after struggling to regain her top form this season.
"One thing's for sure, my opponent played very good today."
The Russian duo of Pavlyuchenkova and Elena Vesnina then beat Bojana Jovanovski and Aleksandra Krunic 6-4 6-0 in the dead doubles rubber to make the final score 3-2.
The two teams were tied at 1-1 after Saturday's singles matches when Jankovic beat Pavlyuchenkova 6-4 6-3 before Kuznetsova levelled the two-day tie by outlasting Ivanovic 6-2 2-6 6-3.
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