In this work, activated carbons (ACs) were prepared from polystyrene-based cation-exchangeable resin (PSI) by a chemical activation with KOH as an activating agent. The surface morphologies were observed by using SEM, and the textural properties were investigated by using nitrogen adsorption at 77 K. From the experimental results, it was found that the well-developed micro- and mesopores were produced by a chemical activation, and the textural properties including specific surface areas and pore volumes were greatly enhanced. The electrochemical behaviors of the ACs showed similar phenomena with that of textural properties. These results indicated that KOH activation played an important role in the changes of surface, and pore structures, resulting in enhancing the electrochemical properties of the ACs prepared in present work.