Two-time Wimbledon champion Kvitova needed just over an hour for an emphatic 6-3, 6-2 win over Julia Goerges at the Porsche Arena in Stuttgart.
Pliskova followed that up with a 7-5, 6-3 win over Angelique Kerber to put the Czechs in firm control going into Sunday's three ties -- two singles and one doubles rubber.
The Czech Republic look well set to continue their impressive recent Fed Cup form having won the title five times in the last seven years.
With the home crowd behind her, Goerges built up a 3-1 lead in the first set only for Kvitova to win the next five games and wrestle control of the match.
In the second rubber, Kerber put in a strong performance, but lost her serve at the crucial moment to lose the first set 7-5.
Pliskova calmly took what was her only chance to break Kerber in the second set with ice-cold precision to seal the victory.
Goerges will now be under pressure to win Sunday's opening rubber against Pliskova to save the Germans from defeat in their home semi.