Thin films of the Ti-W-O system grown by r.f. reactive sputtering from a Ti-W (10%–90% weight) target have been studied by Raman and microraman spectroscopy, X-ray diffraction and scanning electron microscopy with the aim to investigate their microstructural and morphological properties. To this purpose, the kinetics of structural transformations at different temperatures (600 °C, and 800 °C) have been studied, and the effect of Ti on the WO3 lattice has been singled out. The results show that annealing at different temperatures induces a microstructural evolution from the amorphous phase of the as-deposited thin film to WO3 crystalline phases via an intermediate cubic disordered phase of WO3. The effect of Ti on this cubic phase and on the thin film morphology is also investigated with the aid of microraman and scanning electron microscopy analysis. The results show that two distinct phases arise upon long annealing treatments; namely, small crystallites belonging to the WO3 monoclinic phase are dispersed on a layer composed of a disordered cubic WO3 phase with a high Ti content.