Surface activity of thermally evaporated amorphous chalcogenide films of Ge2Sb2Te5 has been investigated. Silver (Ag) is readily deposited on such films from appropriate aqueous ionic solution and Ag diffuses into the films upon irradiation with energetic photons. The composition of Ge2Sb2Te5 thin films and the amount of Ag photo-diffused has been gathered from electron probe micro-analyzer having a wavelength dispersive spectrometer. The composition of the films was found to be very close to the bulk used to deposit films and the amount of Ag photo-diffused was ∼ 0.38at. %. X-ray diffraction and temperature dependent sheet resistance studies have been used for the structural analysis of the bulk alloy, as-deposited, Ag photo-diffused and annealed films at different temperatures. The films remain amorphous after Ag photo-diffusion into the amorphous Ge2Sb2Te5 films. The reflectivity, reflectivity contrast and extinction coefficient of the crystalline and amorphous photo-diffused thin films are presented. The optical band gaps of the amorphous and crystalline photo-diffused (Ge2Sb2Te5)100−xAgx=0.38 phase change thin films have also been calculated from absorption data using UV–VIS spectroscopy.