Silver (Ag) substituted ZnO thin films were successfully deposited onto glass substrates by spray coating technique. Structure, morphology, and optical properties were evaluated by X-ray diffractometer (XRD), scanning electron microscopy (SEM), and UV-Vis spectrophotometer, respectively. XRD spectra had polycrystalline wurtzite structure; SEM images showed that thin films had different surface morphology at different Ag doping concentration. From transmittance spectra, thin films transparency decreased as well as band gap energy along with increase of Ag doping concentration. Methylene blue (MB) solution was used as a pollutant in the photodegradation studies. Under UV light irradiation, the optimal Ag doping is 25%, with 83% of the decolorizing efficiencies after 3 h irradiation time and apparent constant (kapp) about 9.69 × 10−3 min−1