Australian Open semifinalist Karolina Pliskova won the first point for the Czechs against Romania after easing past Mihaela Burzanescu 6-1, 6-4 on an indoor hard-court in Ostrava.
But Simona Halep won the second singles by routing Katerina Siniakova, the star of last year's final victory against the United States, 6-4, 6-0.
Pliskova and Halep, both former world No. 1s, will meet in the key first reverse singles on Sunday.
Romania is trying to beat the Czechs and reach the Fed Cup semifinals for the first time.
In Asheville, the U.S. came back to split the opening singles with Australia.
Ashleigh Barty gave Australia a good start in its bid to end a 35-year losing drought to the U.S. by hitting 10 aces past Sofia Kenin in winning 6-1, 7-6 (2).
But Madison Keys then took only an hour to defeat Kimberly Birrell, playing her first tie in three years, 6-2, 6-2.
In Liege, Caroline Garcia returned to the Fed Cup for the first time since the 2016 final to overcome Alison Van Uytvanck 7-6 (2), 4-6, 6-2 and give France the first point against Belgium.
Alize Cornet made it 2-0 after defeating Elise Mertens 7-6 (6), 6-2.
Belarus, a finalist in 2017, took control against Germany in Braunschweig after Aliaksandra Sasnovich beat Tatjana Maria 7-6 (3), 6-3, and Aryna Sabalenka dispatched Andrea Petkovic 6-2, 6-1.
Belrarus is one win away from avenging losing to Germany 3-2 last year in Minsk.