In this work, hierarchical mesoporous Zn–Ni–Co–S–rGO/NF microspheres have been prepared by hydrothermal, sulfurization, and subsequent calcination process. The effect of different sulfurization time on the morphology and capacitance of composites was tested. The high electrochemical performance of (Zn–Ni–Co–S–rGO/NF) composite was obtained when the sulfurization time was 3 h (Zn–Ni–Co–S–rGO/NF-3h), where a specific capacitance of 627.7 F/g at 0.25 A/g and excellent rate capability of about 97.8% capacitance retention at 2 A/g after 4000 cycles were achieved. Moreover, an asymmetric supercapacitor fabricated by (Zn–Ni–Co–S–rGO/NF-3h) composite and activated carbon (AC) as the positive and the negative electrodes, respectively, showed a high energy density of 75.96 W h/kg at a power density of 362.49 W/kg with a remarkable cycle stability performance of 91.2% capacitance retention over 5000 cycles. This incredible electrochemical behavior illustrates that the hierarchical mesoporous Zn–Ni–Co–S–rGO/N-3h microsphere electrodes are promising electrode materials for application in high-performance supercapacitors.