The superior capability of gemini surfactant (GS) in the preparation of hierarchically porous carbons via high-internal-phase emulsion (HIPE) template followed by pyrolysis was confirmed in this work. Polymerized HIPEs (polyHIPEs) of phenol-formaldehyde resin were prepared by cross linking the continuous phase of HIPEs stabilized by GS. Nonionic surfactant and cationic surfactant were also selected to stabilize HIPE for comparison. From scanning electron microscope observations, polyHIPEs with open-cell pore architectures were obtained with GS as emulsifier(polyHlPEs-GS) and the derived carbon foams (carboHlPEs-GS) well retained the original pore architectures, whereas polyHlPEs obtained using contrastive surfactants showed closed-cell porous structures and notable differences were observed for the derived carboHlPEs. Nitrogen adsorption/desorption measurements indicated that polyHlPEs-GS and carboHlPEs-GS both exhibited hierarchically porous architectures with much higher surface areas (SA) than those of the corresponding contrast samples. Mercury intrusion porosimetry results indicated that 7 carboHlPEs-GS possessed higher SA and higher porosity than that of the contrast samples. The open-cell pore architecture and high SA are favorable to many applications, like energy storage. carboHlPE-GS expectably showed a higher capacitance than that of contrast samples when used as the electrode material of supercapacitor.