Czech captain Petr Pala has made two changes to the team which beat Russia in last year's final.
Lucie Safarova and the now-retired Kveta Peschke drop out with Iveta Benesova and Barbora Zahlavova-Strycova coming in to join Kvitova and Lucie Hradecka.
With their number one player Andrea Petkovic out of action with a stress fracture in her back, the Germans will be led by Sabine Lisicki in the World Group I first-round tie in Stuttgart.
Anastasia Pavlyuchenkova has pulled out of Russia's team to entertain Spain. She is resting a shoulder problem. Fresh from shocking Serena Williams at the Australian Open, Ekaterina Makarova steps in to join a strong line-up, also featuring Maria Sharapova, Svetlana Kuznetsova and Nadia Petrova.
The Spanish will be under the leadership of Arantxa Sanchez Vicario for the first time. She has picked Maria Jose Martinez Sanchez, Carla Suarez Navarro, Arantxa Parra-Santonja and Nuria Llagostera Vives in her first team.
2009 and 2010 champions Italy have Francesca Schiavone and Flavia Pennetta back for their home clash with Ukraine. Both missed last season's semi-final defeat to Russia, but they return to a team which also features Australian Open quarter-finalist Sara Errani and doubles specialist Roberta Vinci.
Ukraine will start as big underdogs on the clay of Biella. They will be led by world number 88 Kateryna Bondarenko.
In the other first-round tie, Serbia will have former world number one Jelena Jankovic in their ranks for the trip to Belgium, but not Ana Ivanovic.
With Kim Clijsters opting out for the Belgians, much will rest on the shoulders of Yanina Wickmayer for the hosts in Charleroi.
All the World Group first-round ties will take place on February 4-5.