In waterlogged paddy soils, cadmium (Cd) can be precipitated as cadmium sulfide (CdS) under reductive environment, thereby limiting the absorption of Cd by plants. Multiple environmental factors (such as water, pH, and Eh) played a role in the control of Cd mobility and bioavailability. In this study, we investigated the influence of the solar irradiation on the photodissolution of synthetic CdS-montmorillonite composites (CdS-M) in solution and the stability of Cd in natural soil. The release kinetic of Cd2+ showed that after the irradiation of simulated sunlight, CdS-M composites became less stable compared to the dark control. The solar irradiation seemed to enhance the release of Cd2+ from CdS significantly and continuously. Electron paramagnetic resonance (EPR) and quenching experiments confirmed that the photogenerated holes, ?O2? and ?OH, were possibly involved in the photo-induced release of Cd2+, while the holes was primarily responsible for the reaction. Irradiation under alkaline solution or the presence of DOM, PO43?, CO32?, and urea markedly inhibited the photodissolution process of CdS. The photo-mediated activation of Cd was further confirmed in paddy soil under natural sunlight, with a nearly threefold increase in concentration of extractable Cd during the 15 days of irradiation. This study highlights the importance of photochemical transformation of Cd in the environmental water and soil.