The emission and Fourier transformation infrared spectra of freshly prepared porous silicon(PS) and the silicon wafer were examined. Increasing temperature generally led to a decrease in the emission intensities of the PS samples, however, the freshly prepared sample showed an unusually large and sudden increase in its emission intensity at the specific temperature at which the hydrogen ion conductivity in the silicon wafer increased. The O-H vibrations of the silicon wafer also showed a sudden decrease at the same temperature. These results are consistent with the assumption that the luminescence of fresh PS comes from the carrier bound exciton in its confined nanostructure. The emission and Fourier transformation infrared spectra of freshly prepared porous silicon (PS) and the silicon wafer were examined. Increasing temperature generally led to a decrease in the emission intensities of the PS samples, however, the freshly prepared sample showed an unusually large and sudden increase in its emission intensity at the specific temperature at which the hydrogen ion conductivity in the silicon wafer increased. The OH vibrations of the silicon wafer also showed a sudden decrease at the same temperature. These results are consistent with the assumption that the luminescence of fresh PS comes from the carrier bound exciton in its confined nanostructure.