The decomposition of AgCl due to ultraviolet and X-ray irradiation was investigated by X-ray Photoelectron Spectroscopy (XPS). Samples were prepared from freshly made AgCl powder either directly from the powder or by melting AgCl onto a platinum substrate, the latter giving significantly higher XPS intensities than the former. The AgCl was exposed only to weak red light prior to irradiation. The results after irradiation indicated a broadened Cl 2p doublet which was resolved into and unbroadened and unshifted Cl 2p doublet and a Cl 2p doublet shifted to a higher binding energy (2.6 eV). Similar results were found for the Cl 2s line. The results thus indicate the presence of a less electro-negative form of Cl on the surface of AgCl after irradiation. The Ag lines were neither broadened nor shifted within the precision of the measurements (0.2 eV). With increasing time of irradiation the intensities of the Ag lines decreased. Possible forms of this photo-induced Cl and the relationship to the photographic process will be discussed.