The fate of ubiquitous microplastics (MPs) is largely influenced by dissolved organic matter (DOM) in aquatic environments, which has garnered significant attention. The reactivity of DOM is reported to be greatly regulated by molecular weights (MWs), yet little is known about the effects of different MW DOM on MP aging. Here, the aging behavior of polystyrene MPs (PSMPs) in the presence of different MW fulvic acids (FAs) and humic acids (HAs) was systematically investigated. Under ultraviolet (UV) illumination, O/C of PSMPs aged for 96 h surged from 0.008 to 0.146 in the lower MW FA (FA <1kDa ) treatment, suggesting significant PSMP aging. However, FA exhibited a stronger effect on facilitating PSMP photoaging than HA, which can be attributed to the fact that FA <1kDa contains more quinone and phenolic moieties, demonstrating a higher redox capacity. Meanwhile, compared to other fractions, FA <1kDa was more actively involved in the increase of different reactive species yields by 50−290%, including •OH, which plays a key role in PSMP photoaging, and contributed to a 25% increase in electron-donating capacity (EDC). This study lays a theoretical foundation for a better understanding of the environmental fate of MPs.