Novel hierarchical porous NiMoS4 microspheres with high electrochemical performance was successfully prepared using a facile one-step hydrothermal method. The dual application of porous NiMoS4 microspheres in energy harvesting and storage (i.e., dye-sensitized solar cells (DSSCs) and supercapacitors (SCs), respectively) is explored. In contrast to NiS2 nanosheets, MoS2 nanosheets and Pt counter electrodes (CEs), the NiMoS4 microspheres CE demonstrated the lowest charge transfer resistance and highest electrocatalytic activity for the I[Formula: see text]/I− redox couple reaction. The NiMoS4-based DSSC showed a higher power conversion efficiency (8.9%) even than that of Pt-based DSSC (8.7%) under simulated standard global AM 1.5[Formula: see text]G sunlight (100[Formula: see text]mW[Formula: see text]cm[Formula: see text]). As an electroactive material for SCs, the assembled NiMoS4//AC asymmetric supercapacitor showed excellent specific capacitance (118.7[Formula: see text]F[Formula: see text]g[Formula: see text] at 1[Formula: see text]A[Formula: see text][Formula: see text], high energy density of 42.2[Formula: see text]Wh[Formula: see text]kg[Formula: see text] (with a power density of 799.2[Formula: see text]W[Formula: see text]kg[Formula: see text], and superior cycling durability with a specific capacitance retention of 79.5% after 9000 cycles at 3[Formula: see text]A[Formula: see text]g[Formula: see text].