Using magnetron sputtering, followed by post calcination TiO2, WO3, and TiO2/WO3 layered films were prepared using magnetron sputtering and followed by post calcination. The film structures and morphologies were checked using XRD, Raman spectroscopy, FE-SEM, XPS, and UV-Vis spectroscopy. The TiO2 and WO3 films are of anatase and orthorhombic structures. The WO3 underlayer of the TiO2/WO3 film grows in [002] direction, almost perpendicular to substrates. Compared with the TiO2 film, the TiO2/WO3-layered film effectively absorbs near-UV light. The photocurrent of layered TiO2/WO3 film is much higher than that of TiO2 film under UV light illumination. The photoelectrocatalytic activity of the films was evaluated in two-electrode photocatalytic reactor, which is assisted by bias voltage. It is seen that PEC activity of TiO2/WO3 film is almost four times higher than pure TiO2 film. Summarily, the TiO2/WO3-layered film with dual-function of anti-UV light and high PEC activity was prepared using facile magnetron sputtering.