<p>The influence of CoMoO₄/Co₃O₄ heterojunction and the interlayer synergistic effect on the morphology and electrochemical performance of composite electrode materials for supercapacitors was explored in this paper. Co₃O₄, CoMoO₄, and CoMoO₄/Co₃O₄ were synthesized on the surface of nickel foam (NF) via a solvothermal synthesis combined with heat treatment. Subsequently, CoMo-LDH was uniformly coated through a secondary solvothermal process. The results indicate that during the material construction process, the growth of CoMoO₄/Co₃O₄ has a pivotal function in promoting its development. It facilitates the formation of a three-dimensional hierarchical nanoflower structure, which results in an increased specific surface area, creating numerous active sites, thereby significantly enhancing electrochemical performance. CoMo-LDH@CoMoO₄/Co₃O₄ exhibited excellent performance due to the synergistic effect of consistent raw material ratios and the superior three-dimensional hierarchical nanoflower structure. Density functional theory calculations confirm the metallic nature of the heterojunction, which synergizes with the nanoflower morphology to facilitate charge transfer. In a three-electrode system, the specific capacitance was found to be 2170.8 mF cm⁻² at 1 mA cm⁻², with inherent impedance and transfer impedance of 0.827 Ω and 0.234 Ω, respectively. Meanwhile, an asymmetric supercapacitor was developed with the prepared CoMo-LDH@CoMoO₄/Co₃O₄ and activated carbon. At a power density of 800.4 µW cm⁻², the energy density was 93.3 µWh cm⁻². After 9000 cycles, its capacitance retention was 85.6%, with Coulombic efficiency stable at 100%.</p>