In this work, the activated carbons (ACs) with high micropores were synthesized from the polystyrene (PS) with KOH as activating agent. And the influence of activation temperature on porosity of the ACs studied was investigated. The porous structures of ACs were characterized by nitrogen adsorption at 77K using BET and D-R equations, and MP and BJH methods. The weight loss behaviors of the samples impregnated with KOH were also monitored using thermogravimetric analyzer (TGA). As a result, it was found that the samples could be successfully converted into ACs with well-developed micropores. From the results of pore size analysis, it was confirmed that elevated activation temperature does lead to the formation and deepening of microstructures without significant change in mesostructures. A thermogravimetric study showed that KOH could suppress the thermal decomposition of the sample, resulting in the increase of carbon yields.