A modified sol-gel method was used to prepare cobalt doped silica thin film with a cobalt content of 10, 20 and 30 mol% (10Co, 20Co and 30Co). The prepared films were annealed at different temperatures in the range 400-1,000 C, and their structural evolution examined. The mixed valence cobalt oxide, Co3O4, crystallizes only in the sample with the higher cobalt content, while cobalt silicate is the only crystalline phase detected in the sample 10Co and 20Co. Both the cobalt content and the temper- ature of heat treatment resulted to affect the nature of cobalt species dispersed in the silica matrix. The 30Co was selected for further investigations by FTIR spectroscopy to follow the structural evolution of 30Co film as function of the temperature and UV-Vis to get information on the cobalt valence state. The optical gas-sensing properties of 30Co films, containing Co3O4 as the major cobalt phase, were studied through the measuring of the film transmit- tance in dry air and in presence of dry air containing var- iable concentrations of polluting gases, CO and NO2. The 30Co samples resulted to be highly sensitive to CO at room temperature. An explanation for the CO sensing charac- teristics, at low temperature, was proposed by referring to the physisorption-related mechanics of CO.