Plastic products widespread in natural water can be broken into smaller-sized microplastics (MPs, < 5 mm) under light irradiation, thermal degradation and biodegradation, posing a serious threat to aquatic ecosystems and human health. This perspective concludes that MPs can generate reactive oxygen species (ROS) through initiation, propagation and termination steps, which can attack the polymer resulting in the photoaging and breakdown of C–C and C–H bonds under ultraviolet (UV) irradiation. Free radical generation and weathering degree of MPs depend on their physicochemical properties and environmental conditions. In general, UV irradiation and co-existed MPs can significantly accelerate MP photoaging. With plentiful chromophores (carbonyl, carboxyl and benzene rings, Dissolved organic matter (DOM) mainly absorbs photons (300–500 nm) and generates hydrated electrons, ³DOM* and ROS, which may affect MP photoaging. However, whether DOM may transfer the electron and energy to MPs under UV irradiation, affect ROS generation of MPs and their photoaging pathway are inadequately studied. More studies are needed to elucidate MP photoaging pathways and mechanisms, consider the influence of stabilization capacity, photosensitization and photoionization of DOM as well as their competitive light absorption with MPs, which provides valuable insights into the environmental behavior and ecological risk of MPs in natural water.