The first-round series opens Saturday with Kvitova, No. 8 in the world, playing Jarmila Gajdosova followed by the No. 9-ranked Stosur going against Lucie Safarova.
On Sunday, the singles partners are switched and Stosur goes against Kvitova in a Top 10 pairing that will be important to deciding the best-of-five series. Kvitova is 16-5 overall in Fed Cup singles matches. That includes a 5-1 mark in boosting the Czech to the 2012 title. Stosur is 23-9 in Fed Cup competition.
Gajdosova and Safarova would go in the fourth singles match.
If those matches are split 2-2, the series would be decided by a doubles match pitting Australians Ashleigh Barty and Casey Dellacqua against Czechs Andrea Hlavackova and Lucie Hradecka.
The matches are to be played indoors on a hard court in Ostrava. The series winner advances to April's Fed Cup semifinals against the winner of a series between Italy and the United States.
The Czech Republic is looking for a third consecutive Fed Cup title, a feat not accomplished since Spain turned the trick in 1992-93. Before that Czechoslovakia, from which the Czech Republic came, won three straight over 1983-85, however. Australia owns seven Fed Cup titles, the most recent in 1974.