The 38-year-old was thwarted by compatriot Arianna Errigo in her bid for an amazing fourth consecutive Individual Foil gold at the Games.
No woman has achieved that in any individual Olympic event - and the only men to have done it are Carl Lewis in the long jump (1984-96) and fellow American Al Oerter in the discus (1956-68).
Vezzali, who carried Italy's flag at the Opening Ceremony, made it through to the semi-finals, taking her unbeaten Olympic run to 18 contests since she lost the 1996 final.
It then came down to the world's top four - three of them Italians - and number one Vezzali was beaten 15-12 by fourth-ranked Errigo, only the third time the 24-year-old had defeated her in 16 fights.
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