The internal surface of porous silicon layers was chemically modified with various silanes: hexamethyldisilazane, methylchlorosilanes ((CH3)(m)SiCl4-m, m = 1, 2, 3), methyltriethoxysilane and tetraethoxysilane. The chemical composition of these layers was studied by IR reflectance spectroscopy. From the IR spectra the effective dielectric function epsilon(eff) of the porous layers was determined and analyzed. Tn order to study the effect of surface modification on the luminescence properties PL spectra of the modifed layers were recorded. The chemical stability in ambient air and water-saturated atmosphere at 50 degrees C and 90 degrees C was investigated.