Toxic toluene gas caused enormous harm to human health, and the traditional method to deal with this puzzle is using physical adsorption, which just transfer the toluene from one medium to another. Photocatalysis has great potential to mineralize toluene into CO2 under visible light irradiation, but their applications have been limited by difficulties in preparing efficient photocatalysts with fine crystallite size, considerable visible light response, and large surface area to contact with toluene gas. To address this problem, we have developed a film composed of W-doped TiO2 nanofibers to mineralize toluene under visible light irradiation. The electrospinning preparation route allows incorporation of up to 50 wt% of W in substitutional positions of titanium atom in the anatase network. The W-doped TiO2 nanofibers behave finer crystallite size, stronger visible light absorbance, and larger surface area comparing with pure TiO2 nanofibers. The nanofiber structured morphology on the quartz tube promotes the reaction rates for the gas-phase photo-oxidation of toluene. The concentrations of the produced CO2 keep steady during the photodegradation process, indicating the practicality and operability for the whole experiment. This research is conducive to the development of novel photocatalytic materials to efficiently mineralize toxic gas pollutants including toluene for practical application.