The fabrication of energy storage electrode materials with high specific capacitance and rapid charge-discharge capability has become an essential and major issue of concern in recent years. In the present work, sphere-shaped interconnected interlinked binder-free nickel sulfide (NiS) grown on the surface of a three-dimensional nickel foam (3DNF) was fabricated by a one-step solvothermal method under optimized synthesis conditions, including different solvents, amounts of sulfur, and experimental reaction times. The fabricated binder-free SS-NiS@3DNF-E electrodes were characterized by a range of spectroscopic and microscopic techniques and further evaluated for their comparative electrochemical supercapacitive performance in half-cell assembly cells. The optimized sphere-shaped interconnected interlinked binder-free SS-NiS@3DNF-E-3 electrode showed an outstanding specific capacitance of 694.0 F/g compared to SS-NiS@3DNF-E-1 (188.0 F/g), SS-NiS@3DNF-E-2 (470.0 F/g), and SS-NiS@3DNF-E-4 (230.0 F/g) as well as excellent cycling stability up to 88% after 6700 continuous charge-discharge cycles, with an energy density of 24.9 Wh/kg at a power density of 250.93 W/kg. The obtained results demonstrate that the interconnected interlinked binder-free NiS@nickel electrode is a potential candidate for energy storage applications.