In this study, activated carbon fibers (ACFs) with high surface area and pore volume have been modified by Ni doping and fluorination. The surface modified ACFs were characterized by BET surface area, SEM/EDS, XRD, and Raman spectroscopy. The changes in pore structure and surface properties of these modified ACFs were correlated with hydrogen storage capabilities. After fluorination treatment, although the micropore volume of ACF was decreased, amounts of hydrogen storage were found to increase. Additionally, micropore volume on ACFs was found to be unchanged with Ni doping, hydrogen storage capacities were considerably increased due to the effect of catalytic activation of nickel. Though fluorination of ACFs increases hydrogen affinity, the effect of catalytic activation of nickel is more prominent, and thus led to better hydrogen storage. Hence, it was concluded that hydrogen storage capacity was related to micropore volumes, Pore size distribution (PSD) and surface properties of ACFs as well as specific surface areas. (c) 2006 Elsevier B.V. All rights reserved.