Towards rapid development of lightweight, flexible, and even wearable electronics, a highly efficient energy-storage device is required for their energy supply management. Graphene fiber-based supercapacitor is considered as one of the promising candidates because of the remarkable mechanical and electrical properties of graphene fibers. However, supercapacitors based on bare graphene fibers generally suffer a low capacitance, which certainly restricts their potentially wide applications. In this work, hierarchically structured MnO2 nanowire/graphene hybrid fibers are fabricated through a simple, scalable wet-spinning method. The hybrid fibers form mesoporous structure with large specific surface area of 139.9 m2 g−1. The mass loading of MnO2 can be as high as 40 wt%. Due to the synergistic effect between MnO2 nanowires and graphene, the main pseudocapacitance of MnO2 and the electric double-layer capacitance of graphene are improved simultaneously. In view of the practical demonstration, a highly flexible solid-state supercapacitor is fabricated by twisting of two MnO2/graphene fibers coated by polyvinyl alcohol/H3PO4 electrolyte. The supercapacitor exhibits a high volumetric capacitance (66.1 F cm−3, normalized by the total volume of two fiber electrodes), excellent cycling stability (96% capacitance retention over 10,000 cycles), high energy and power density (5.8 mWh cm−3 and 0.51 W cm−3, respectively).