Pironkova began 2012 representing Bulgaria at the Hopman Cup losing to Petra Kvitová. Pironkova and her partner Grigor Dimitrov defeated Tomáš Berdych and Kvitová in doubles. Despite their win, the team of Bulgaria lost to the Czech Republic (1–2), after Pironkova and Dimitrov lost their singles matches. Afterward, their team was victorious against Denmark 2–1. They scored a victory over the United States, but finished second in Group A and didn't qualify for the final.