Hematite (α-Fe₂O₃) has garnered significant research interest for supercapacitor applications, but capacity fading and limited cyclic life remain serious challenges. In this context, the present research provides a comprehensive study of the factors that significantly impact charge kinetics within the electrode and at the solid/electrolyte interface. By integrating structural and electrochemical analyses, this study offers an effective strategy to enhance the capacity of α-Fe₂O₃ nanoparticles through rigorous scientific analysis and identification of various qualitative and quantitative factors that influence charge storage capacity. A simple one-step co-precipitation method was adopted to synthesize porous α-Fe₂O₃ nanoparticles. The quantitative analysis of charge kinetics demonstrated the domination of diffusion-controlled charge storage as the main contributor to the total charge storage. The α-Fe₂O₃ nanoparticles-based electrode delivered a high energy density of 24.6 Wh kg⁻1 at an impressive power density of 478.7 W kg⁻1. Additionally, it displayed a capacity retention of 79 % over 10,000 cycle operations. The choice of electrode material and the superior porous nanoarchitecture have proven to be advantageous for high-performance supercapacitor applications, offering fast electron/ion transport.