W-doped titanium dioxide is a promising candidate material for applications ranging from UV-VIS light photocatalytic reactions to catalyst support in proton-exchange membrane fuel cells, depending on the doping content. The present study reports on the possibility to synthesize substitutional Ti1-xWxO2 thin films with 0 <= x <= 1 by magnetron co-sputtering from Ti and W metallic targets. Two routes were investigated starting from 1) crystalline titanium tungsten alloys deposited in non-reactive (pure Ar) mode, and 2) amorphous titanium tungsten oxides deposited in reactive (Ar + O2 atmosphere) mode. The structure and phase stability after air annealing at 550 °C has been investigated by X-ray Diffraction (XRD). X-ray Reflectivity (XRR) was used to determine the change in film mass density upon annealing. Films of the non-reactive mode series could not be successfully fully oxidized into Ti1-xWxO2 form. For the reactive mode film series, ternary Ti1-xWxO2 oxides were obtained after air annealing and the crystal structure was changed from anatase to rutile with increasing W content in the range 0-33 at.%. Films with higher W content (0.33< x <= 1) eventually crystallized in the WO3 triclinic structure. Photo-electrodes were elaborated from the deposited thin films on FTO coated glass, and they all showed photo-response when tested in acid solution, under UV-VIS illumination. Among the doped materials, the Ti0.92W0.08O2 thin film showed the highest photo-current.