To render supercapacitors (SCs) more practical, they must exhibit high cycling stability of at least ten thousand cycles with commercial-level mass loadings, which differentiates them from batteries. Metal-organic framework (MOF)-based electrode materials are promising for use in energy storage systems owing to their excellent electrochemical performance. In this study, we report the electroactivities of bimetallic MOFs (Co, Ni, and Co–Ni) using a single-step, facile, and cost-effective hydro/solvothermal method. To optimize their performances, we develop a general strategy for analyzing various binder-free MOFs. Additionally, the effects of the reaction time, reaction temperature, solvents, and elements (Ni, Co, and H2BDC) on the surface morphology and electrochemical performance are investigated. Based on an analysis of the electrochemical properties of all the synthesized electrode materials, the optimal electrode delivers an ultrahigh areal capacity of 2621 µAh cm−2 (297.1 mAh g−1) at 7 mA cm−2, with a high-rate capability of 82.5 % even at 40 mA cm−2. The optimized Co–Ni MOF electrode is employed as a positive electrode to fabricate an aqueous hybrid SC (HSC) with an activated carbon-coated nickel foam electrode as a negative electrode. The as-fabricated HSC exhibits excellent electrochemical properties with exceptional cycling stability (120k cycles) and improved rate capability (60 %). Additionally, we identify factors that contribute to improved redox reactions in the Co–Ni MOF-based HSC, such as the role of Co–Ni MOFs in the redox reaction and the influences of other structural parameters on charge storage and transfer processes. Our aim is to further understand the underlying mechanisms of the improved redox reactions and thus obtain new insights into the design and optimization of Co–Ni MOF-based HSCs. Finally, the energy storage properties of the HSC are validated by using it to power different electronic devices. The promising outcomes obtained in this work can serve as a basis for the future practical implementation of high-energy-density HSCs with high mass loadings and charging rates. SynopsisTo render the practicability of hybrid supercapacitor (HSC) with enhanced energy storage properties, we investigate the electroactivities of bimetallic metal-organic frameworks (MOFs) (Co, Ni, and Co–Ni) using a single-step, facile, and cost-effective hydro/solvothermal method. To optimize their performances, a general strategy is developed for analyzing various binder-free MOFs. Additionally, the effects of the reaction time, reaction temperature, solvents, and elements (Ni, Co, and H2BDC) on the surface morphology and electrochemical performance are studied. In addition, we validate the energy storage properties of the HSC by using it to power different electronic devices. The promising outcomes obtained in this study can serve as a basis for the future practical implementation of high-energy-density HSCs with high mass loadings and charging rates.