<p>Nanoparticles (NPs) are ubiquitous and persistent contaminants in aquatic environments, where they undergo complex transformations that alter their intrinsic properties. A critical environmental process is the formation of an "NPs-EPS corona" through the adsorption of extracellular polymeric substances (EPS) secreted by microorganisms. The behavior, biotoxicity, and fate of NPs in the aquatic environment can be significantly impacted by the EPS. Many research findings reveal that the EPS corona endows NPs with dynamic, biologically active interfaces, altering surface chemistry and core reactivity. These changes enhance interactions with environmental components (e.g., nutrients, contaminants, biota), driving transformations in elemental cycles and triggering trophic-level responses across nutritional gradients. Critically, activated NPs-EPS corona propagate through food webs via energy transfer, leading to toxicant accumulation in apex predators and posing significant risks to ecosystem integrity and human health. This review was trying to explore the interactions of EPS on the surface of NPs, and map the transport pathways utilized by NPs, enabling predictive behavior and environmental risk assessment of NPs-EPS corona in aquatic systems.</p>