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High-dispersion polystyrene (PS) microspheres with monodispersity were successfully synthesized by the non-emulsification polymerization method, and three-dimensional (3D) photonic crystals of PS microspheres were fabricated by electrophoretic self-assembly (EPSA). The metal nickel inverse opal structure (IOS) photonic crystal, of which the structural thickness can be freely adjusted via electrochemical deposition (ECD), and subsequently, MnS/MoS2/Ni-IOS specimens were also prepared by ECD. Excellent specific capacitance values (1880 F/g) were obtained at a charge current density of 5 A/g. The samples in this experiment were tested for 2000 cycles of cycle life and still retained a reasonably good level of 76.6% of their initial capacitance value. In this study, the inverse opal structure photonic crystal substrate was used as the starting point, and then the microelectrode material for the MnS/MoS2/Ni-IOS supercapacitor was synthesized. Our findings show that the MnS/MoS2/Ni-IOS microelectrode makes a viable technical contribution to the design and fabrication of high-performance supercapacitors.