Dolonc will see her first Fed Cup action Saturday against the Slovaks' Dominika Cibulkova and is to face Daniela Hantuchova, who holds Slovak records for Fed Cup appearances (25) and wins (32) in the second singles match Sunday.
She's also penciled in to play doubles, with Aleksandra Krunic, in Sunday's final match against the Jana Cepelova and Magdalena Rybarikova.
Serbia would usually call on Ana Ivanovic and Jelena Jankovic -- both ranked in the Top 30 -- for singles duty in Fed Cup play. But Ivanovic has a shoulder problem and Jankovic also pulled out due to injury.
Bojana Jovanovski, who is 4-3 in Fed Cup singles, was made the Serbs' No. 1 and meets Hantuchova in Saturday first match before Dolonc sees her first Fed Cup action. Jovanovski is to play Cibulkova in Sunday's first match.
Serbia fell to the Czech Republic in last year's final but has never won a Fed Cup. The Slovaks took the 2002 title but were part of Czechoslovakian teams that won five Fed Cup titles.
The best-of-five series takes place on an indoor hard court in Nis, Serbia, with the winner earning a semifinal spot in April against the winner of the Japan-Russia series in Moscow.