Developing highly efficient heterostructured photocatalysts with robust redox ability is of great significance to wastewater purification. Herein, a novel Z-scheme AgI/Sb2WO6 heterojunction was successfully constructed via a chemical-precipitation method. The Z-scheme system can serve as a highly efficient photocatalyst for degradation of organic pollutants in water. Under visible light illumination, the degradation efficiency of rhodamine B and tetracycline over the optimal Z-scheme heterojunction can achieve 95% in 12 min and 80% in 8 min, which is 10.8 and 11.4 times higher than that over single Sb2WO6, respectively. Interestingly, low amounts of Ag0 can be generated and attached on the surface of Sb2WO6 during the photocatalytic process, further enhancing the photocatalytic activity of the Z-scheme heterojunction. Based on theoretical calculations, the interfacial internal electric field (IEF) can facilitate the photoexcited electrons at the conduction band (CB) of AgI to consume the photoexcited holes at the valence band (VB) of Sb2WO6, which greatly promotes the Z-scheme charge transfer path. Quenching experiments and electron spin resonance analyses demonstrate superoxide radicals play a major role in the photocatalytic reactions. The concept of constructing a Z-scheme heterojunction photocatalyst with efficient interfacial charge transfer shall provide a design guide for wastewater purification.