GeS6 chalcogenide amorphous film was deposited on glass substrate via PLD (pulsed laser deposition) technique. The performance and structure of the film was characterized by XRD (X-ray diffraction), SEM (Scanning Electron Microscopy), EDS (Energy Dispersive Spectroscopy), optical transmission spectra, and Raman spectra, etc. The GeS6 amorphous film was irradiated by 532 nm linearly polarized light, and its photo-induced darkening was investigated. The results showed that the GeS6 chalcogenide amorphous film was smooth and compact with uniform thickness and combined with the substrate firmly, and its chemical composition was in consistency with the bulky target. When laser energy was fixed, the transparence of the film declined with the increase of the laser irradiation time. Obvious photo-induced darkening and relaxation phenomenon of the film after laser irradiation were observed in this investigation.