Serbia's Jankovic, who became the country's first grand slam champion when she won the Wimbledon mixed doubles title in 2007, won more points in the match than her Russian opponent, but slipped to a shock loss.
"Ekaterina was coming from qualies and had a few matches under her belt, and she played very well. I felt asleep and in slow motion," world number 13 Jankovic told the WTA's official website.
"It just wasn't my day. I look forward to resting and coming back strong in 2012."
Poland's Agnieszka Radwanska will need to beat Lucie Safarova to secure her place at the season-ending WTA Tour Finals in Istanbul later this month, after the Czech battled back to earn a 6-7 (9-7) 6-4 6-3 triumph against Spain's Arantxa Parra Santonja.
Jelena Jankovic
Jelena Jankovic
Jelena Jankovic
Jelena Jankovic
Jelena Jankovic
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