Rodionova's debut for the Australian Fed Cup team was in Kharkov, Ukraine, on 24 April 2010, where she opened the tie with an emphatic win over Alona Bondarenko, coming back from losing the first seven games. This gave Australia a commanding 1–0 lead that set up Sam Stosur for two straight forward wins in her singles matches for a 3–0 defeat of Ukraine, securing Australia's place in World Group I for 2011. Rodionova also partnered with Rennae Stubbs to win the final rubber of doubles after Alicia Molik won her substituted singles match, giving Australia a decisive 5–0 victory in the tie.