TiO2and W:TiO2 thin films have been prepared by a chemically modified sol-gel technique, that implies hydrolysis and condensation of tetraethylortotitanate in the presence of a polymer dissolved in ethanol. Oxide-polymer films were deposited by dip-coating. Annealing at 500°C results in nanosized structurally stable oxides films. For doping tungsten(V)ethoxide was used in concentration that led to a final W/Ti atomic ratio of 1/33, 5/33, 10/33. The morphological and structural characteristics of thin films were studied through microraman, GIXRD, SEM and TEM. A microstructural comparison between pure and doped TiO2 layers is reported. Ethanol and methanol sensing properties are tested.