Environmentally persistent free radicals (EPFRs) are defined as organic free radicals stabilized on or inside particles. They are persistent because of the protection by the particles and show significant toxicity to organisms. Increasing research interests have been attracted to study the potential environmental implications of EPFRs. Because of their different physical forms from conventional contaminants, it is not applicable to use the commonly used technique and strategy to predict and assess the behavior and risks of EPFRs. Current studies on EPFRs are scattered and not systematic enough to draw clear conclusions. Therefore, this review is organized to critically discuss the current research progress on EPFRs, highlighting their occurrence and transport, generation mechanisms, as well as their environmental implications (including both toxicity and reactivity). EPFR formation and stabilization as affected by the precursors and environmental factors are useful breakthrough to understand their formation mechanisms. To better understand the major differences between EPFRs and common contaminants, we identified the unique processes and/or mechanisms related to EPFRs. The knowledge gaps will be also addressed to highlight the future research while summarizing the research progress. Quantitative analysis of the interactions between organic contaminants and EPFRs will greatly improve the predictive accuracy of the multimedia environmental fate models. In addition, the health risks will be better evaluated when considering the toxicity contributed by EFPRs.