In this study, direct templating method was employed for preparation of mesoporous carbon materials with different pore structure. In order to control pore structure, reaction time of surfactant/silicate which played a role of template was varied. According to increase of reaction time, larger pore size, smaller pore volume, lower pore connectivity and rougher pore surface were observed. From an investigation of supercapacitor performance, it was concluded that higher pore connectivity resulted in more improved rate performance in spite of smaller pore size. Especially, the carbon electrode of 2h reaction time delivered a high capacitance of 102Fg−1 and capacitance per area (13.0μFcm−2), which indicated an efficient utilization of the available pores. Furthermore, the electrode exhibited a low resistance of 2.4Ωcm2, which was comparable to ordered mesoporous carbon electrodes.