Reduced graphene oxide/carbon black (rGO/CB) hybrid films with different carbon black (CB) contents are prepared by a simple vacuum filtration method. The CB particles evenly distribute between the graphene layers, not only preventing the compact restack of rGO sheets but also providing electrical contact between the base planes of rGO sheets. As expected, the as-prepared rGO/CB hybrid film shows enhanced rate capability when compared with rGO film. Furthermore, a solid-state flexible supercapacitor has been constructed with the optimized rGO/CB hybrid film by using polyvinyl alcohol (PVA)/H2SO4 gel as electrolyte and Au coated PET film as current collector and mechanical support. The solid-state flexible supercapacitor shows a specific capacitance of 112 F g−1 at a scan rate of 5 mV s−1, and excellent rate performance with a specific capacitance of 79.6 F g−1 at a high scan rate of 1 V s−1. Moreover, the flexible solid-state supercapacitor exhibits good cycling stability with capacitance retention of 94% after 3000 cycles in normal state plus 2000 cycles in bent state.