Rationally fabricating the hybrid nanostructures with a distinctive surface and internal properties is substantial due to their multifunctional features in energy storage and catalysis applications. Generally, the battery-like supercapacitor materials experience low energy density and inferior cyclic stability issues due to their intercalation/ deintercalation process. To address this problem, the dichalcogenides (WSe 2 and MoSe 2 ) were hybridized with a battery-like material (NiCo 2 O 4 ), which effectively changed the diffused-controlled to the surface-controlled process and enhanced the energy density and cyclic stability features. The pentagon core−hexagon ring-structured NiCo 2 O 4 nanoplate with MoSe 2 hybrid structures presents excellent electrochemical features with a specific capacity of 857 C g −1 at 1 A g −1 and retains 98% initial capacity after 5000 cycles at 30 A g −1 , which is higher than that of pure NiCo 2 O 4 and NiCo 2 O 4 /WSe 2 materials. The asymmetric supercapacitor device (NiCo 2 O 4 /MoSe 2 //activated carbon) provides an energy density of 69 W h kg −1 at a power density of 1280 W kg −1 and withstands an excellent cyclic stability of 95% after 10,000 cycles at 30 A g −1 . Moreover, a preliminary electrochemical analysis was performed to evaluate the CO 2 electro-reduction property of the hybrid structures using an H-type cell in a 0.5 M choline chloride electrolyte. The hybridization of MoSe 2 enhanced the CO 2 electro-reduction properties in the NiCo 2 O 4 material in terms of high current density, low overpotential, smaller equivalent series resistance, charge transfer resistance, and increased electrochemical surface area. These excellent supercapacitors and CO 2 electro-reduction performance provide valuable insights into the design and optimization of nonprecious hybrid materials for multifunctional applications and render a viable approach to enhance the internal properties of various materials in the future. KEYWORDS: supercapacitors, CO 2 electro-reduction, NiCo 2 O 4 /WSe 2 , NiCo 2 O 4 /MoSe 2 , diffusive-and surface-controlled processes, core−ring structure