Porous silicon (PSi) structure was formed at different current densities in the range of 5–60mA/cm 2 by the electrochemical anodization of PSi wafers etching in HF for 30min. The PSi was characterized by X-ray diffraction studies. The PSi samples prepared at current densities above and below 30mA/cm 2 show PL spectra with asymmetric and overlapped peaks. On the top surface as well as inside the pores of this PSi structures the precursor sol–gel was incorporated by the spin coating technique and SnO 2 was formed by heating at 400°C in air. Peaks pertaining to PSi along with those corresponding to SnO 2 were observed, which confirmed SnO 2 formation as thin film on the PSi surface. The PL spectra of SnO 2 /PSi structure aged for two months indicated a reduction in PL intensity but remained constant afterwards. SnO 2 not only modifies the nature of silicon nanopores but also is expected to influence the interface states in SnO 2 /PSi junction.