In this work, Ag-doped ZnO nanoparticles are obtained via pulsed laser ablation of the Ag-coated ZnO target in water. The ratio of Ag dopant in ZnO nanoparticles strongly depends on the thickness of the Ag layer at the ZnO target. Synthesized nanoparticles were characterized by XRD, XPS, SEM, EDS, ICP-OES, and UV–VIS spectrophotometry to obtain their crystal structure, elemental composition, morphology and size distribution, mass concentration, and optical properties, respectively. The photocatalytic studies showed photodegradation of methylene blue (MB) under UV irradiation. Different ratios of Ag dopant in ZnO nanoparticles influence the photodegradation rate. The ZnO nanoparticles doped with 0.32% silver show the most efficient photodegradation rate, with the chemical reaction constant of 0.0233 min−1. It exhibits an almost twice as large photodegradation rate compared to pure ZnO nanoparticles, showing the doping effect on the photocatalytic activity.