Generation of environmentally persistent free radicals (EPFRs) on solid particles has recently attracted increasing research interest. EPFRs potentially have high reactivity and toxicity. However, the impact of EPFRs on organic contaminant behavior is unclear. We hypothesized that EPFRs in biochars can degrade organic contaminants and play an important role in organic contaminant behavior. We observed obvious degradation of p-nitrophenol (PNP) in the presence of biochars, through the detection of NO3(-) as well as organic byproducts. The extent of PNP degradation was correlated to the intensity of EPR signals of biochar particles. tert-Butanol (a •OH scavenger) did not completely inhibit PNP degradation, indicating that •OH could not fully explain PNP degradation. The decreased PNP degradation after tert-butanol addition was better correlated with reduced PNP sorption on biochars. PNP degradation through the direct contact with EPFRs in biochar particles could be an important contribution to the PNP concentration reduction in the aqueous phase. The coating of natural organic matter analogue (tannic acid) on biochars did not considerably inhibit PNP degradation, suggesting the ability of biochars to degrade PNP in soil and natural water. Similar EPFR-promoted degradation was observed for five different types of biochars and one activated carbon, as well as one additional chemical (p-aminophenol). Therefore, organic chemical degradation by EPFRs in biochars can be a common process in the environment and should be incorporated in organic chemical fate and risk studies.