Activated carbon fibers (ACFs) with high surface area and pore volume were modified with metal Ni impregnation and fluorination and investigated hydrogen storage properties by volumetric method. Micropore volume values of ACFs obtained from surface modification with Ni impregnation and fluorination were decreased 9 and 35 %, respectively. Hydrogen storage capacities of fluorinated ACFs were slightly changed, on the other hand, that of Ni impregnated ACF was considerably increased. It means that hydrogen was not only adsorbed on ACF surface, but also on Ni metal surface by means of dissociation. Although the microphone volume of ACF modified with fluorination was decreased, its hydrogen storage were found not to be changed compared with fresh ACF. These results indicated that the surface of ACF after fluorination modification may be strongly attracted hydrogen due to high electronegativity of fluorine. Therefore, it was proven that hydrogen storage capacity was related with micropore volume and surface property of carbon materials as well as specific surface area.