The technique of step-by-step optically-induced solid state reaction (OSSR) of Ag with As33S67 amorphous Alms, which has allowed to design films with exact silver concentration, is reported. The host As33S67 films were photodoped by consecutive dissolving thin (similar to 10 nm) layers of silver, which resulted in a single-phase optically homogeneous film. It was possible to prepare amorphous Ag-A (AS(0.33)So(0.67))(100-x) films With defined silver concentrations of amorphous solid solutions ranging from 1 to 41 at. %. We have analyzed the effect of the silver doping in the host material on optical, thermal and mechanical properties. and its structure by means of optical spectroscopy, temperature-modulated differential scanning calorimetry, microhardness measurements and Raman spectroscopy, respectively. The photodoped films with a silver concentration close to 25 at. %. i.e. with composition of the stoichiometric AgAsS2 compound, showed distinct features of their optical, thermal, mechanical properties and their structure.