At present, binary bimetallic sulfides are widely studied in supercapacitors due to their high conductivity and excellent specific capacitance (SC). In this article, NiCo-S nanostructured hybrid electrode materials were prepared on nickel foam (NF) by using a binary metal–organic skeleton as the sacrificial template via a two-step hydrothermal method. Comparative analysis was carried out with Ni-S and Co-S in situ on NF to verify the excellent electrochemical performance of bimetallic sulfide as an electrode material for supercapacitors. NiCo-S/NF exhibited an SC of 2081 F∙g−1 at 1 A∙g−1, significantly superior to Ni-S/NF (1520.8 F∙g−1 at 1 A∙g−1) and Co-S/NF (1427 F∙g−1 at 1 A∙g−1). In addition, the material demonstrated better rate performance and cycle stability, with a specific capacity retention rate of 58% at 10 A∙g−1 than at 1 A∙g−1, and 75.7% of capacity was retained after 5000 cycles. The hybrid supercapacitor assembled by NiCo-S//AC exhibited a high energy density of 25.58 Wh∙kg−1 at a power density of 400 W∙kg−1.