With the continuous advancement of high-tech industries, how to properly handle pollutants has become urgent. Photocatalysis is a solution that may effectively degrade pollutants into harmless molecules. In this study, we synthesized single crystalline Zn2SnO4 (ZTO) nanowires through chemical vapor deposition and selective etching. The chemical bath redox method was used to modify the ZTO nanowires with Ag nanoparticles to explore the photocatalytic properties of the nanoheterostructures. The combination of the materials here is rare. Optical measurements by photoluminescence (PL) and UV–Vis show that the PL spectrum of ZTO nanowires was mainly in the visible light region and attributed to oxygen vacancies. The luminescence intensity of the nanowires was significantly reduced after modification, demonstrating that the heterojunction could effectively reduce the electron-hole pair recombination. The reduction increased with the increase in Ag decoration. The conversion from the UV–Vis absorption spectrum to the Tauc Plot shows that the band gap of the nanowire was 4.05 eV. With 10 ppm methylene blue (MB) as the degradation solution, ZTO nanowires exhibit excellent photodegradation efficiency. Reusability and stability in photodegradation of the nanowires were demonstrated. Photocatalytic efficiency increases with the number of Ag nanoparticles. The main reaction mechanism was confirmed by photocatalytic inhibitors. This study enriches our understanding of ZTO-based nanostructures and facilitates their applications in water splitting, sewage treatment and air purification.