A two-step hydrothermal route was employed to fabricate a ZnMoO4/CoO nanohybrid supported on Ni foam. The ZnMoO4/CoO nanohybrid shows a three-dimensional criss-crossed structure. The specific surface area is enhanced from 45 m2 g-1 of ZnMoO4 to 67 m2 g-1 of the ZnMoO4/CoO nanohybrid. Furthermore, the existence of electroactive CoO is in favor of reducing the charge transport resistance. The ZnMoO4/CoO nanohybrid electrode possesses a high capacitance of 4.47 F cm-2 at 2 mA cm-2, which is much higher than those of ZnMoO4 (1.07 F cm-2) and CoO (2.47 F cm-2). The ZnMoO4/CoO nanohybrid electrode also exhibits an ultrahigh cycling stability with 100.5% capacitance retention after 5000 cycles at 20 mA cm-2. In addition, an asymmetric all-solid-state supercapacitor was assembled using the ZnMoO4/CoO nanohybrid as the positive electrode and exfoliated graphite carbon paper as the negative electrode. The asymmetric supercapacitor exhibits a superior energy density of 58.6 W h kg-1 at a power density of 800 W kg-1 and a considerable cycling stability with 81.8% capacitance retention after 5000 cycles at 5 A g-1. The ZnMoO4/CoO nanohybrid demonstrates its tremendous advantages and possibilities as a positive electrode material in energy storage applications. Moreover, for a better understanding of the electrochemical behavior, a combined study of experimental measurements and density functional theory calculations is also applied to illustrate the high-performance of the ZnMoO4/CoO nanohybrid.