The complicated preparation process and low energy density of polyaniline (PANI)-based electrodes limit their wide applications in flexible energy storage devices. In this work, a reduced graphene (rGO)-wrapped polyaniline nanofiber network (PANI-NFN)/oxidized carbon cloth (OCC) (rGO@PANI-NFN/OCC) composite was prepared by a facile impregnation method using reactive templates of MnO₂ on the surface of OCC. The as-prepared rGO@PANI-NFN/OCC composite exhibited a high area specific capacitance of 4438 mF cm⁻² and maintained an initial capacitance of 88.2% after 3000 GCD cycles. It can be used as an independent electrode to construct flexible solid-state supercapacitors (FSSCs), and the FSSCs based on rGO@PANI-NFN/OCC also exhibit a high energy density of 117.9 μW h cm⁻² and 88.39% retention after 500 bending cycles, which shows a great prospect for flexible energy storage device applications. The enhanced performance of rGO@PANI-NFN/OCC composites is mainly attributed to the synergistic effect of PANI-NFN structures with a large specific surface area and a rGO wrap layer to reduce the swelling and shrinking of PANI.