The facile design and fabrication of nanoarchitectured binary transition metal oxide electrode materials are essentially required for the advancement of highperformance supercapacitors (SCs). Herein, we prepared an oxygen-vacant NiMoO 4 (Ov-NiMoO 4 ) hollow sphere via a simple hydrothermal approach and subsequent heat treatment under an argon atmosphere. In particular, the oxygen vacancy is confirmed by using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), Raman, and differential reflectance spectroscopy (DRS) UV-Vis spectra studies. Furthermore, the generation of the oxygen vacancy could enhance the electrical conductivity and improve Faradaic redox sites. Significantly, the Ov-NiMoO 4 hollow sphere depicts a larger specific capacity (C sp ) of 496 mA h g À1 at 1 A g À1 than the bare-NiMoO 4 (b-NiMoO 4 ; 279 mA h g À1 ) thermally treated under air. Furthermore, the hybrid SC (HSC) is fabricated based on the Ov-NiMoO 4 //activated carbon, revealing a high specific capacitance (C s ) of 120 F g À1 and providing a large energy density (ED) of 37.49 W h kg À1 and power density (PD) of 36.61 kW kg À1 . Moreover, the HSC shows considerable cyclic stability of ~91.14% over 20 000 cycles. The results divulge that the poor crystallinity and the introduction of oxygen vacancies play a vital role in enhancing the charge-storage capability of the materials.