Abstract: Photocatalysis technology is an effective and environmentally friendly method for removing indoor volatile organic pollutants. In this work, WO₃ nanowires with hierarchical nanowire structure were in-situ grown on tungsten web by hydrothermal method, and PtPd alloy nanoparticles were uniformly loaded on WO₃ nanowires by chemical reduction method. The self-supported PtPd/WO₃ composite photocatalyst was successfully constructed and applied to the oxidation decomposition of toluene, a typical indoor pollution gas. When the molar ratio of PtPd was 9:1, the photocatalytic removal of toluene by prepared PtPd/WO₃ nanowire was the best. The novel and unique WO₃ hierarchical nanowire structure provides an ideal three-dimensional interface for the anchoring adsorption of gaseous toluene. The Schottky junction formed between PtPd/WO₃ promotes the production of a large number of hydroxyl radicals to oxidize toluene, thus realizing its effective decomposition. Under the irradiation of 100 mW/cm² light source, the removal rate of 412 mg/cm³ toluene within 60 min is 98.9%, and the mineralization rate is 90.9%. This work provides a new idea for designing practical photocatalytic materials that can degrade typical air pollutants efficiently.