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A mixture of hydrophilic silicon dioxide (SiO2) and visible-light-reactive tungsten oxide (WOX) has the potential to improve the photocatalytic activity of conventional titanium dioxide (TiO2). This study deposits mixed WOX–SiO2 thin films on TiO2 surfaces by controlling the composition of WOX:SiO2 using radiofrequency sputtering to improve photocatalytic activity and hydrophilicity. The photocatalytic activity is evaluated via the degradation of a methylene blue solution, and hydrophilicity is measured using the water contact angle. In addition, the effect of annealing is determined at 400 °C after deposition. The optical bandgap decreases as the composition of WOX increases and subsequently anneals. The XRD measurements show that polycrystalline monoclinic WO3 peaks appear after annealing when the composition of the mixed WOX–SiO2 thin films only consists of WOX. In contrast, monoclinic WO3 (200) appears after adding SiO2. Atomic force microscopy images show that the grain size decreases as the SiO2 content increases. Moreover, the photocatalytic activity of the mixed WOX–SiO2 thin films improves after annealing. In particular, the mixed WOX–SiO2 thin films that are deposited at a sputter power of WOX:SiO2 = 100:50 W demonstrate a remarkable improvement in photocatalytic activity. Furthermore, the water contact angle of the mixed WOX–SiO2 thin films decreases as the SiO2 content increases and after annealing. This proposed approach can be used for high-performance photocatalytic materials and be widely applied for the fabrication of various semiconducting devices.