As 33 S 67−y Se y , where y=0, 16.75, 33.5, 50.25 and 67, amorphous thin films were prepared by a vacuum thermal evaporation technique. The films with known silver concentrations and good optical quality were prepared by thermal vacuum evaporation of a silver film on the top of As 33 S 100−y Se y films with sequential step-by-step optically- and thermally-induced diffusion and dissolution (OIDD) of silver. The range of silver content was x=0–25at.%. The kinetics of OIDD of silver were measured optically by monitoring the change of thickness of the undoped part of the chalcogenide during broadband illumination. Compositions of the reaction products have been determined by scanning electron microscope with energy-dispersive X-ray microanalyser EDS. Optical properties (T,n,Egopt) of thin films were measured and/or calculated by the Swanepoel method [R. Swanepoel, J. Phys. E: Sci. Instrum. 16 (1983) 1214]. The refractive index increase with increasing silver and selenium concentration has been shown. The difference of the refractive index (Δn) between undoped and silver doped films was ∼0.4 and between As 33 S 67 and As 33 Se 67 was films ∼0.42. Non-linear indices of refraction were estimated according to Tichy’s formula [H. Ticha, L. Tichy, J. Optoel, Adv. Mat. 4 (2002) 381]. The values of non-linear refractive index grew with increasing silver and selenium content. The difference of optical bandgap, ΔEgopt, between undoped As 33 S 67 and fully doped films with Ag and Se was ∼1eV. Raman spectroscopy showed a decrease in S–S or Se–Se bonds with increasing silver content.