Saturday's first singles bout will pit German Sabine Lisicki against Czech veteran Iveta Benesova, and that match will be followed by one between the world No. 2 Wimbledon champion Kvitova and Julia Goerges.
Sunday's singles will pit Kvitova against Lisicki and Benesova versus Goerges, while Sunday's doubles match currently calls for a German tandem of Anna-Lena Groenefeld and Angelique Kerber to take on a Czech pairing of Lucie Hradecka and Barbora Zahlavova Strycova.
The best-of-five tie will be staged on an indoor hardcourt at Porsche Arena.
The Czechs are captained by Petr Pala, while the two-time champion Germans are led by Barbara Rittner. The Czechs are 5-1 all-time versus Germany.
The winner in Stuttgart will face the Italy-Ukraine victor in the Fed Cup semifinals in April.
The Czech Republic captured a sixth Fed Cup title last year by beating Russia 3-2 in the final. Five of the Czech titles came when they were part of the former Czechoslovakia.