Ag/AgCl structures with specific morphology were synthesized via solvothermal method in ethylene glycol. Structures were characterized by SEM, EDS, XRD and DRS techniques and their photochemical and photoelectrochemical properties were examined. For the first time, the indirect method of chlorine disproportionation products sensing was applied together with reactions specific to hydroxyl radicals and hypochlorite ions to establish which reactive species are photogenerated in aqueous suspensions of the examined material. The results showed that the main species produced during irradiation are hypochlorous acid and hydrochloric acid. Moreover, the activity of silver chloride structures in the spectral range of visible light was confirmed. Photocurrent response reveals the material photoactivity up to 550 nm. The collected data indicate, that the photoactivity of Ag/AgCl should be considered as its photochemical transformations (photocorrosion) rather than photocatalytic processes.