The effect of chemical treatments of porous silicon in organic solvents on its nanostructural and optical features was investigated. When the porous Si was dipped in the organic solvent with various PH values, the morphological, chemical, and structural properties of the porous silicon was sensitively affected by the chemical conditions of the solvents. The size of silicon nanocrystallites in the porous silicon decreased from 5.4 to 3.1 nm with increasing pH values from 1 to 14. After the samples were dipped in the organic solvents, the Si-O-H bonding intensity was increased while that of Si-H bonding decreased. Photoluminescence peaks shifted to a shorter wavelength region in the range of 583 to 735 nm as the pH value increased. PL intensity was affected by the size as well as the volume fraction of the nanocrystalline silicon in the porous silicon.