The energy band structure and corresponding carrier transfer efficiency are crucial roles in photocatalysis performance, especially involving the volatile organic compounds (VOCs) degradation in gas-solid phase photocatalytic systems. Herein, we reported a S-scheme heterojunction photocatalyst of Ag@WO3/TiO2. The photocatalytic experiments display that Ag@WO3/TO2 (denoted as Ag@h-WT) possesses almost 94% of toluene removal rate and nearly 90% mineralization after 60min irradiation under simulated sunlight, superior to those of pure TiO2 and h-WO3 as well as binary WO3/TO2 heterojunction. The improved photocatalytic activity is mainly ascribed to i) the formation of S-scheme heterojunction. ii) The Ag nanoclusters promotes the carrier separation and broadens the light absorption region.