Rolli was initially sent by his father to study under Giuseppe Antonio Caccioli, later becoming a pupil of the renowned fresco painter Domenico Maria Canuti. He developed a style that closely followed Canuti’s footsteps, specializing in large-scale fresco cycles. Much of Rolli's career was defined by a close partnership with his brother, Antonio Rolli (1643–1695). While Giuseppe focused on the figurative elements, Antonio specialized in quadratura (architectural illusionism). Their most notable joint achievements include, in Bologna, Palazzo Pepoli Campogrande, Casa Ranuzzi and Palazzo Isolani. As a solo artist, Giuseppe Rolli, decorated several major ecclesiastical ceilings, including the Basilica of San Bartolomeo e Gaetano and the Oratory of San Giovanni Battista dei Fiorentini (1699). His reputation also led to international recruitment by the Prince of Baden to paint mythological themes.