Herein, the single-phase Ni-based bimetallic spinel oxide (NiM2O4, M = Mn, Fe, Co) nanoparticles are successfully synthesized by sol–gel method and coated on a carbon cloth substrate to form flexible electrodes for supercapacitor applications. The effects of transition metal activity, calcination temperature, surface, and textural properties on the electrochemical properties of spinel electrode materials are demonstrated. It is found that lowering the calcination temperature results in a decrease in crystallite size and particle size, leading to an increase in surface area and pore volume. X-Ray absorption spectroscopy reveals the presence of Mn2+/3+, Fe2+/3+, and Co2+/3+ in materials. According to the electrochemical studies, NiMn2O4 electrode in Na2SO4 electrolyte exhibits electrical double-layer capacitance behavior, while NiFe2O4 and NiCo2O4 electrodes in KOH electrolyte exhibit pseudocapacitive behavior. All electrode materials have low solution resistance and charge transfer resistance. NiCo2O4 provides the highest specific capacitance (85.60 F g−1 at 2.5 A g−1) followed by NiFe2O4 and NiMn2O4. It seems likely that the high electrochemical activity of Co2+/3+ and small particle size of NiCo2O4 nanoparticles play an important role in improving the redox process and charge transfer, which may enhance the electrochemical performance of this electrode material.