To prevent the evident agglomeration of silver nanoparticles during processing, this study reduced silver nanoparticles in pseudo-thermoplastic polyvinyl alcohol (PT-PVA) water solutions using the synchronous chemical reduction method. The PT-PVA coating could protect the silver nanoparticles to avoid agglomeration, allowing the silver nanoparticles to disperse uniformly in the PT-PVA. According to the particle size, TEM and UV-Vis analyses, the reduction of silver nanoparticles in PT-PVA solutions produced silver nanoparticles/PT-PVA films that had small particle size without agglomeration. Conversely, silver nanoparticles were added directly into PT-PVA, tended to have obvious agglomeration during the preparation process.