Microplastics (MPs) are emerging pollutants and pose a significant threat to marine ecosystems. Although previous studies have documented the mechanisms and toxic effects of aging MPs in various environments, the impact of the marine environment on MPs remains unclear. In the present study, the aging process of polystyrene (PS) in seawater was simulated and the changes in its physicochemical properties were investigated. Our results showed that the surface of the PS eroded in the seawater, which was accompanied by the release of aged MPs with a smaller size. In situ optical photothermal infrared microspectroscopy revealed that the mechanism of PS aging was related to the opening of the carbonyl group and breaking of the bond between carbon and benzene removal. To verify the toxic effects of aged PS, Caenorhabditis elegans was exposed to PS. Aged PS resulted in a greater reduction in locomotion, vitality, and reproduction than virgin PS. Mechanistically, aged PS led to oxidative stress, high glutathione s-transferase activity, and high total glutathione in worms. Together, our findings provided novel information regarding the accelerated aging of PS in seawater and the increased toxicity of aged PS, which could improve our understanding of MPs’ ecotoxicity in the marine environment.