Kvitova, No. 8 in the world, earlier this year won a pair of singles matches in the quarterfinals against Germany and two more in helping the Czechs defeat Italy in the semifinals as the Czech Republic looks to repeat as Fed Cup champion. She is 10-0 in cup play over the last two years.
Serbia edged Belgium and Russia, which lost to the Czechs in the 2011 final, in earning its first Fed Cup finals spot.
The best-of-five final is scheduled for a hard court in Prague.
Kvitova goes against Ivanovic in Sunday's first reverse singles before a Safarova-Jankovic matchup. The placement of Kvitova in the second and third matches in the schedule follows the strategy Czech captain Petr Pala used in the quarterfinals and semifinals.
The fifth match of the series is doubles with Serbs Bojana Jovanovski and Aleksandra Krunic going against the Czech team of Lucie Hradecka and Andrea Hlavackova.