The 2011–12 season saw her win the Tauberbischofsheim World Cup for the second time in a row, as well as the St Petersburg World Cup. At the European Championships in Legnano she lost in the quarter-finals to Russia's Larisa Korobeynikova. She qualified to the 2012 London Olympics as a member of the top-ranked Italian team. In the individual event she was seeded fourth and she received a bye in the first round. For her first Olympic bout she crushed Lebanon's Mona Shaito 15–2. In the table of 16 Germany's Carolin Golubytskyi took an early 8–3 lead against her, but Di Francisca managed to stop the onslaught. At 6–8 she was bridging the gap when she accidentally hit Golubytskyi under the mask with the bell guard of her foil. Her opponent stumbled to the ground and the bout had to be interrupted for medical care. Golubytskyi never regained her initial advantage and was defeated 15–9. Di Francisca prevailed over Japan's Chieko Sugawara on the same score. She had a narrow 11–10 victory in the semi-finals against Nam Hyun-hee, striking the winning hit in overtime. She then met fellow Italian Arianna Errigo in the final. After a slow start Di Francisca built a 7–3 lead in the second period, but Errigo managed to come back and the bout went into overtime with 11 all. Di Francisca received priority and scored immediately to win the Olympic title.