Sunlight-oxidative ageing is a common and critical process for microplastics (MPs) in aquatic environments. O₂^•−, ¹O₂, and •OH generation has been widely proven in this process, which can alter metal speciation based on its reduction and oxidation potential. Herein, chemical speciation of Ag mediated by polystyrene (PS) MPs was determined under simulated sunlight irradiation. The O₂^•− generation on the PS MPs surfaces is the vital factor for Ag⁺ reduction, regardless of acid or base conditions. The ¹O₂ and •OH are dominant factors, and ¹O₂ played a more important role than •OH for its higher formation amount, causing oxidative dissolution of newly formed Ag⁰ nanoparticles (NPs). The Ag NPs can hetero-aggregate with PS MPs through electrostatic interactions with O–containing groups (C–O, C–OH and CO), and co-precipitate from the water phase. This hetero-aggregation can stabilize Ag NPs by inhibiting Ag NPs surface photooxidation and suppressing Ag⁺ release. Transformation of Ag species (from Ag⁺ to Ag⁰ NPs) mediated by sunlight with PS MPs significantly suppressed acute toxicity of Ag⁺ to Escherichia coli, Selenastrum capricornutum, Daphnia magna and zebrafish. This study emphasized that PS MPs play an important role in the speciation, migration and toxicity of Ag⁺ in freshwater environments.