Nanocrystalline n-typeTiO2 thin film is coated on high porosity porous silicon (PS) by sol-gel spin coating method. TiO2 was infiltrated into the pores of PS and thereby making active layer. X-ray diffraction (XRD), Scanning electron microscopy (SEM), Photoluminescence (PL) and Fourier transform infrared spectroscopy (FTIR) studies have been carried out to examine the characteristics of TiO2/PS structure. XRD results confirm the formation of high quality TiO2 tetragonal structure on PS surface and along with PS peak, anatase & rutile peaks of TiO2 were also observed. The grain sizes calculated for TiO2 thin film, Porous Silicon and TiO2/PS are 85 nm, 32 nm and 25 nm respectively. SEM images reveal that the pores are filled by TiO2 showing island like structures. Blue and Green PL emission peaks were observed at an excitation of 410 nm in PL spectrum. The presence of Ti-O-Ti, Si-O-Si & Si-O-Ti bands were observed from FTIR study. From the results it is observed that the described structure can be used for sensor applications.