Metal organic frameworks (MOFs) have attracted great attention as adsorptive material for hydrogen storage because of their exceptionally high specific surface areas and chemically tunable structures. Fine structural properties of central chromium atoms in MIL-53 have been studied using XANES and EXAFS spectroscopies in the present work. Fourier transformed EXAFS (extended X-ray absorption fine structural) spectra of MIL-53 showed that the bond distance of Cr–O (first shell) was 1.959Å with a coordination number of about 4.7. The pre-edge XANES (X-ray absorption near edge structural) spectra of Cr atoms in MIL-53 exhibit an absorbance feature around 5988eV for the 1s to 3d transition which was forbidden by the selection rule in the case of perfect octahedral symmetry. However, the sharp feature at 6008eV and well defined shoulders at 6003eV were due to the dipole-allowed of 1s to 4pxy electron transition. These features of XANES spectra identified the existence of Cr(III) in MIL-53(Cr) structure. The synthesized MIL-53(Cr) adsorbs 1.45 wt% hydrogen measured at 77K and 60bar while after modification with Pd-loaded activated carbon (AC), the hydrogen adsorption capacity was increased to 1.92 wt% due to spillover effect of H2 molecules. The heat of adsorption was also calculated from both high-pressure hydrogen adsorption data using modified D-A model and from the low-pressure hydrogen adsorption data using the van't Hoff equation.