Meso/macroporous activated carbon fibers (ACFs), containing mesopores and macropores in addition to micropores, were prepared from carbonization and steam-activation of the phenolic resin fibers blended with a small amount (0.1 wt %) of an organic nickel complex. Conventional (microporous) ACF as reference sample, mainly composed of micropores, was also prepared from pure phenolic resin fibers without any agent. The electric double-layer capacitance of these ACFs was measured in propylene carbonate containing 1.0 mol dm(-3) LiClO4 (1.0 M LiClO4/PC). The correlation between the capacitance and the BET (Brunauer-Emmett-Teller) specific surface area of the microporous ACFs showed the nonlinearity due to strong ion-sieving of micropores. The double-layer capacitance of the meso/macroporous ACFs was higher than the microporous ACF, because the ion-sieving effect of micropores was relaxed by the presence of meso/macropores. The relaxation by the meso/macropores was enhanced for the cation adsorption or the high current density measurement. These results confirm that the presence of many meso/macropores promotes the formation of an effective double layer or fast transfer of ions in the microporous structure.