In this paper, we demonstrated the synthesis and electrochemical properties of macro-/ microporous carbon foams (MMCFs) for application as supercapacitor electrode materials. By using Span 80 and Tween 80 as emulsifiers, resorcinol/formaldehyde solution as aqueous phase, and 1iquid paraffin as oil phase, an O/W emulsion was obtained. Macroporous carbon foams were prepared by the polymerization of the emulsion, followed by drying and carbonization. The macroporous carbon foams then were activated at 1273 K by using KOH as an activated agent to obtain MMCFs. The resultant MMCFs were characterized by scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) analyzer. The results indicate that the MMCFs have specific surface areas of 529-670 m2/g, total pore volumes of 0.27-0.33 cm3/g and possess dual pore size distributions with macropore sizes of 0.5-5.0 μm and micropore sizes of 1.72-1.86 nm dependent on the specific experiment parameters. The hierarchical pore structure is propitious to decreases the diffusion resistance of electrolyte and accelerate the ion transfer within the pore channel, and thus improve the electrochemical properties of MMCFs. The electrochemical properties of the MMCFs have been investigated by cyclic voltammetry (CV) and galvanostatic charge-discharge with a three-electrode system in electrolyte of 6 mol/L KOH solution. The CV curves of the MMCFs show quite rectangular curve shape without observation of obvious oxidation-reduction evolution peaks, suggesting a typical nonfaradic adsorption/desorption reaction. The MMCFs present linear galvanostatic charge-discharge curve under the current densities of 1.0-4.0 A/g and their specific capacitance values are 89-110 F/g. The MMCFs has good electrochemical performance and they are good candidates as electrode materials for supercapacitors.