We have studied effects of hydrogen-termination on optical properties of porous Si. The hydrogen concentration in the samples was controlled by photochemical etching after the electrochemical anodization. Transmission electron microscopy examination shows that the size of Si crystallites in porous silicon ranges from 3 to 10 nm and no significant size changes occur by the photochemical etching process. The PL spectra, the PL excitation spectra, and the picosecond PL decay rate were sensitive to the photochemical etching process. Spectroscopic analysis suggests that the radiative recombination occurs at the near-surface region of the Si crystallites.