The activated carbons(AC) with high specific area were used widely as the electrode materials for the supercapacitors. Here we report the synthesis of nano-activated carbon electrode materials with different pore size distributions by vibration milling at room temperature. The size of the active carbon particles decreased from 20 to 30~50nm depended on the experimental conditions, and the particle distribution became more reasonable. The influence of important preparation technique condition(milling time， exciting frequency， vibration additive) on the nm-AC microstructure were found. Based on SEM, AFM, XRD and BET tests, we experienced the microstructure (crystalline, surface area, pore volume, pore size) of the nm-AC materials. It is found that manganese oxide as milling additive has more notable influence on improvement of material microstructure. Active carbon samples can gain more mesopores in shorter milling time and higher exciting frequency is useful to sample microstructure improvement. In short time，we can gain mesopore structure suitable nano-activated carbon electrode materials through vibration milling method.