Hristova is a five-time world champion and also claimed silver at Beijing 2008, but she was denied Olympic gold again thanks to an impressive performance from three-time junior world champion Vorobieva.
The 21-year-old lost the first period after being pushed off the mat but came back to pin her opponent - a rarity in Wrestling - in the second to seal a shock victory.
Maider Unda had earlier won bronze to claim Spain's first-ever Wrestling medal. Kazakhstan's Guzel Manyurova won the division's other bronze.
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