This study focuses on preparing composite hierarchical porous carbon nanofiber film that includes ZnO and MnO2. Using electrospinning technology, hierarchical porous structure was introduced into the nanofibers, enhancing energy density through the synergistic effect of zinc oxide and manganese dioxide. The zinc-manganese dioxide co-modified hierarchical porous carbon nanofiber film (ZnMnO-HPC) exhibits outstanding electrochemical performance when used as supercapacitor electrode, with a specific capacity reaching 401.77 C/g at 0.5 A/g, and 201.29 C/g at high current density of 5 A/g. ZnMnO-HPC also exhibits remarkable energy density when assembled with activated carbon electrode into asymmetric capacitor, reaching 38.37 Wh/kg at a power density of 407 W/kg and 19.5 Wh/kg at a power density of 12,800 W/kg, indicating promising applications in the high-energy-density supercapacitor field.