Microplastics (MPs), as plastics with a size of less than 5 mm, are ubiquitously present in the environment and become an increasing environmental concern. The fate and environmental behavior of MPs are significantly influenced by the presence of free radicals. Free radicals can cause surface breakage, chemical release, change in crystallinity and hydrophilicity, and aggregation of MPs. On the other hand, the generation of free radicals with a high concentration and oxidation potential can effectively degrade MPs. There is a limited review article to bridge the fate and environmental behaviors of MP with free radicals and their reactions. This paper reviews the sources, types, detection methods, generation mechanisms, and influencing factors of free radicals affecting the environmental processes of MPs, the environmental effects of MPs controlled by free radicals, and the degradation strategies of MPs based on free radical-associated technologies. Moreover, this review elaborates on the limitations of the current research and provides ideas for future research on the interactions between MPs and free radicals to better explain their environmental impacts and control their risks. This article aims to keep the reader abreast of the latest development in the fate and environmental behaviors of MP with free radicals and their reactions and to bridge free radical chemistry with MP control methodology.