Titanium dioxide (TiO2) thin films have been deposited by DC reactive magnetron sputtering on silicon and quartz substrates with different Ar/O2 ratios in the gas mixture. Substrate temperature was kept constant at 400 °C during the deposition process, and the TiO2 thin films were later annealed at 700 °C for 3 h. The effect of the Ar/O2 ratio in the gas flow and the annealing treatment on the phase composition, deposition rate, crystallinity, surface morphology and the resulting photocatalytic properties were investigated. For photocatalytic measurements, the variation of the concentration of the methylene blue (MB) dye under UV irradiation was followed by a change in the intensity of the characteristic MB band in the UV- Vis transmittance spectra. We report here that the as-grown TiO2 films showed only the anatase phase, whereas after annealing, the samples exhibited both the anatase and rutile phases in proportions that varied with the Ar/O2 ratio in the mixture of gases used during growth. In particular, the annealed TiO2 thin film deposited at a 50/50 ratio of Ar/O2, composed of both anatase (80%) and rutile phases (20%), exhibited the highest photocatalytic activity (30% of MB degradation) compared with the samples without annealing and composed of only the anatase phase.