Abstract: Activated carbon prepared by traditional chemical activation possesses a rich microporous structure, but many tiny pores cannot be utilized for energy storage and may even reduce the graphitization degree of porous carbon, which limits the performance of devices in practical applications. Therefore, how to coordinately control the pore structure and surface chemistry of carbon materials is the key to effectively balancing the microstructure and electrochemical performance of supercapacitor carbon electrode materials. Based on this, acid-base cooperative activation can not only modify the surface chemistry of carbon electrodes, but also effectively regulate the pore structure, accordingly enormously improving the electrochemical behavior of the materials. For this research, taking deashed and pulverized anthraciferous coal as a carbon source, pore formation is carried out by pre-corrosion of the precursor with KOH, subsequently further porous expansion and exterior stability utilizing H₃PO₄ reactivation to prepare super-pure coal-based activated carbon with little mesoporous growth. The results indicate that when co-activated carbon is used as the electrode in electric double-layer capacitors (EDLCs), the abundant network of small mesopores and large micropores can effectively facilitate the diffusion of electrolyte ions, significantly reduce the internal resistance of the device, and rapidly form an electric double layer at the electrode-electrolyte interface, thereby enhancing the high-rate capacity. Moreover, ameliorating surface chemical properties can enhance capacitive invertibility of porous carbon frameworks, enabling it to exhibit stable long-cycle performance. The prepared union-activating porous carbon electrode in 6 mol/L KOH displays an internal resistance as low as 2.40 mΩ, a high capacitance of 214 F/g, and excellent rate performance with the capacity retention rate of 71.79% at 10 A/g. Even more remarkably though, the oxidation resistance of the carbon material is improved owing to the decrease for instable chemical species on the electrode surface. The assembled organic ultracapacitors can stably charge/discharge for long cycles in 1 mol/L Et₄NBF₄/PC, demonstrating good cyclability of 97.55% capacity retention after thousands of cycles. The study has achieved high added value and valid exploitation of anthraciferous coal, while also providing thorough electrochemical views for industrial applications of micro-mesopore carbon in the leading-edge high power energy storage field.