Herein, we report room temperature reduction and covalent grafting of graphene oxide sheets by thiophene derivatives to produce pseudocapacitive electrodes, which are capable of delivering high capacitance (230 F g⁻¹ at 1 mV s⁻¹) and, most important, 100% cycling retention after 5000 cycles. Raman and FTIR spectroscopies confirmed the strong interaction of PTh with rGO in the PTh-g-rGO hybrids.