Kuznetsova, who won last year's French Open, and Ivanovic, No. 23 as of Monday, open the best-of-five series on an indoor hard court in Belgrade. The winning team has a Fed Cup semifinal appointment against either France or the United States in April.
The second singles match sends Russian Alisa Kleybanova, ranked 31st, against Serbian Jelena Jankovic, another former No. 1 who is currently ranked eighth in the world.
Sunday's reverse singles would feature a Top 10 matchup of Kuznetsova meeting Jankovic while Ivanovic goes against Kleybanova.
The fifth match is doubles, with Ivanovic and Jankovic being teamed against Russians Vera Dushevina and Anastasia Pavlyuchenkova.
Russia is looking for its fifth Fed Cup title since 2004. The Russians are 2-0 against Serbian players, but both of those pairings came when Russia played as part of the Soviet Union and Serbia was part of Yugoslavia.
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