The low electron conductivity and scarce electrochemically active sites impede the practical application of bimetal oxides for supercapacitors. Herein, fluorine-doped and oxygen vacancy–enrich NiMoO4 (F-NiMoO4-x) nanosheet arrays are constructed via facile hydrothermal and wet chemical reduction processes on carbon cloth fibers (CFC). The structural and electronic properties in F-NiMoO4-x can be modulated by the synergistic effect of dopant F and O vacancies to boost the electrical conductivity and enhance Faradaic redox sites. The obtained flexible F-NiMoO4-x@CFC as a self-supporting electrode can provide superior areal capacitance of 2.45 F cm−2 at 1 mA cm−2, 6-fold higher than that of pristine NiMoO4@CFC electrode. Moreover, the assembled flexible solid-state asymmetric supercapacitor (ASC) delivers an impressive energy density of 336.5 μWh cm−2 at a power density of 1790 μW cm−2 with a wide voltage window of 1.8 V. Moreover, the ASC can work at different bending angels with an ultralong and stable lifespan.