Microplastics (MPs) will coexist with various pollutants in the environment, but it is not clear whether these pollutants will affect the aging process of MPs. The aging process of polystyrene microplastics (PS-MPs) mediated by Cu²⁺ and Pb²⁺ was investigated in this study. The results showed that the aging rate of PS-MPs mediated by Cu²⁺ and Pb²⁺ were significantly higher than that of ultrapure water (After 7 days of light irradiation, the CI values of aging PS-MPs mediated by ultrapure water, Cu²⁺ and Pb²⁺ increased from 0.030 of original PS-MPs to 0.034, 0.048 and 0.086 respectively). This process may be related to the generation of a large amount of reactive oxygen species, because OH were detected in PS-MPs suspension mediated by Cu²⁺, which were significantly higher than those in ultrapure water, while ¹O₂ mediated by Pb²⁺ were more. However, these photo-aging effects were significantly inhibited by reactive oxygen species (ROS) quencher, which indicated that excessive ROS production was the main reason for metal ions to promote the photo-aging of PS-MPs. In addition, this study reported that excessive ROS will accelerate the formation of carbonyl group on the surface of PS-MPs, and lead to the change of physical and chemical properties of PS-MPs. This study provides new insights for the environmental behavior of MPs under the condition of combined pollution.