Facilitation of the photocarrier separation is a crucial strategy for developing highly efficient photocatalysts in eliminating environmental pollutants. Herein we have developed a new kind of Ag 2 MoO 4 /ZnWO 4 (AMO/ZWO) composite photocatalysts with a Z-scheme mechanism by anchoring AMO nanoparticles onto ZWO nanorods. Multiple characterization methodologies and density functional theory (DFT) calculations were employed to study the performances of the AMO/ZWO heterojunctions as well as the underlying photocatalytic mechanism. Simulated-sunlight-driven photodegradation experiments for removing methylene blue (MB) demonstrates that the 8%AMO/ZWO heterojunction can photocatalytically remove 99.8% of MB within 60 min, and the reaction rate constant is obtained as 0.10199 min -1 , which is enhanced by 6.8 (or 4.9) times when compared with that of pure ZWO (or AMO). On the base of the experimental results and DFT calculations, the enhanced photocatalytic mechanism of the AMO/ZWO heterojunctions was revealed to be the efficient separation of photocarriers via a Z-scheme transfer process. In addition, photodegradion of various organic pollutants over 8%AMO/ZWO was further compared and aimed at incorporating it into industrial application in pollutant removal.