Titanium dioxide (TiO2) is very employed in solar cells due to its interesting physicochemical and optical properties allowing high device performances. Considering the extension of applications in nanotechnologies, nanocrystalline TiO2 is very promising for nanoscale components. In this work, nanocrystalline TiO2 thin films were successfully deposited on porous silicon (PSi) by metal organic chemical vapor deposition (MOCVD) technique at temperature of 550°C for different periods of times: 5, 10 and 15 min. The objective was to optimize the physicochemical and optical properties of the TiO2/PSi films dedicated for photovoltaic application. The structural, morphological and optical properties of the elaborated TiO2/PSi samples were analyzed by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), photoluminescence (PL) and UV-Visible absorption spectroscopy methods. The effect of deposition time on the microstructural properties which influences the optical characteristics of the obtained samples was also examined. The XRD analysis confirms the nanocrystalline structure of the deposited TiO2 composed only by anatase phase. The SEM characterization evidenced an increase in the TiO2 film thickness showing more uniform surfaces as the deposition time rises. Correspondingly, the surface roughness increases with the particle size and film thickness as indicated by AFM studies. The TiO2/PSi/Si sandwich structure evidenced by cross-sectional SEM confirms the good adherence of the TiO2 nanocrystalline film on the porous silicon forming with silicon a composite material. The UV-Vis measurements showed a considerable enhancement in optical absorption of porous silicon after the deposition of TiO2 films. Indeed, the TiO2 coatings deposited on PSi for 15 min with thickness of 200 nm have the best structure quality and exhibit, consequently, the highest absorption. From these interesting results, we demonstrate the viability of the use of the MOCVD as reproducible process for the elaboration of high-quality TiO2/PSi films.