Micropollutants with high ecotoxicological risks are frequently detected in aquatic environments, which has aroused great concern in recent years. Humification is one of the most important natural detoxification processes of aquatic micropollutants, and the core reactions of this process are polymerization and coupling. During humification, micropollutants are incorporated into the macrostructures of humic substances and precipitated from aqueous systems into sediments. However, the similarities and differences among the polymerization/coupling pathways of micropollutants in different oxidative systems have not been systematically summarized in a review. This article reviews the current knowledge on the weak oxidation-induced spontaneous polymerization/coupling transformation of micropollutants. First, four typical weak oxidative conditions for the initiation of micropollutant polymerization reactions in aquatic environments are compared: enzymatic catalysis, biomimetic catalysis, metal oxide oxidation, and photo-initiated oxidation. Second, three major subsequent spontaneous transformation pathways of micropollutants are elucidated: radical polymerization, nucleophilic addition/substitution and cyclization. Different solution conditions are also summarized. Furthermore, the importance of toxicity evolution during the weak oxidation-induced coupling/polymerization of micropollutants is particularly emphasized. This review provides a new perspective for the transformation mechanism and pathways of micropollutants from aquatic systems into sediments and the atmosphere and offers theoretical support for developing micropollutant control technologies. (C) 2019 Elsevier B.V. All rights reserved.