Polypyrrole@cellulose fibers (PPy@CFs) electrode materials are promising candidates in the energy storage. Various strategies have been pursued to improve their electrochemical performance. However, the poor conductivity, specific capacitance, and cyclic stability still hindered its application. Compared with the previous studies, we selected AQS with electrochemical activity as a dopant to improve these defects. It exhibits a high capacitance of 829.8 F g−1 at a current density of 0.2 A g−1, which is much higher than that of PPy@CFs electrode material (261.9 F g−1). Moreover, the capacitance retention of PPy:AQS/p-PTSA@CFs reaches up to 96.01% after 1000 cycles, indicating superior cyclic stability. Therefore, this work provides an efficient strategy for constructing high-performance electrode materials for energy storage.