In this article, we demonstrate the combined effect of photodoping and photoinduced-surface deposition in a bilayer of chalcogenide glass (ChG) and Ag as an alternative method to optically synthesize Ag nanoparticles (AgNP) on the surface of ChG. In our experiment, AgNP formation occurs through two distinct stages: In the first stage, Ag is transported through the As2S3 layer as Ag+ ions, and in the second stage Ag+ ions are photo-deposited as AgNP. The ex situ x-ray photoelectron spectroscopy measurements and AFM observations show photoinduced Ag mass transport and the formation of AgNP.