The Czechs are trying to being the first team to win three consecutive Fed Cup titles since Spain in 1993-95.
Czechs, as part of Czechoslovakia, won three championships over 1983-85. The Slovak Republic Fed Cup team is also in this year's semifinals.
The Czechs are in Palermo, Italy, for a best-of-five series on an outdoor clay court.
Italy won the Fed Cup in 2009 and 2010 but was denied a third consecutive trip to the finals when the Czechs beat them 4-1 in last year's semifinals, with Kvitova winning both of her singles matches.
Kvitova, No. 8 in the world rankings, was given the second singles match Saturday and the first Sunday in the series. She'll go against world No. 12 Roberta Vinci in her first match and open Sunday's play against No. 7-ranked Sara Errani.
Errani and Lucie Safarova open the series with a singles match Saturday. Safarova faces Errani in the fourth singles match.
The winner of the Czech-Italy series moves to the Nov. 2-3 Fed Cup final against either the Slovak Republic or Russia, who have their semifinal in Moscow.