Free radicals (FRs) present in coal dust directly influence the interaction behavior between lung cells and dust particles. FRs are atoms or groups containing unpaired electrons, with strong chemical reactivity and a short lifespan. FRs which are quite persistent in natural environments, termed environmentally persistent free radicals (EPFRs), have recently received much attention as new environmentally hazardous substances. EPFRs present on coal dust serves as an active intermediary to catalyze reactive oxygen species (ROS) production by oxygen molecules endangering mine workers’ health. Many EPFR species may be bonded to the particle surface or trapped within the particle during coalification and can be modified with progressive size reduction through cutting at the mining face or crushing/pulverization in the plant. This study measured EPFRs for lignite, sub-bituminous, and anthracite coal dust at various sizes. We especially focused on EPFRs for submicron coal dust prepared by cryogenic methods. The outcome of this study will directly improve the free radical-dependent toxicity quantification and ultimately contribute to the size-dependent coal dust toxicity quantification.