XANES and X-ray photoelectron spectra (XPS) using synchrotron radiation as a X-ray source were applied for analysis of silicon crystalline irradiated by 5 keV deuterium ions. Si K-edge XANES spectra recorded either by a photocurrent or electron yield modes clearly showed a new absorption peak in addition to the absorption due to surface SiO2. In Si Is XPS spectra, on the contrary, no clear peak or shoulder was detected except SiO2 species. Taking into account that Si K-edge XANES reflects the electron transition from Si Is to np (empty bound state), the new absorption peak is very likely caused by the generation of localized electronic bond between Si and D in the vicinity of the damaged region in the irradiated Si.