The persistent free radicals (PFRs) in biochar can play a crucial role during biochar’s utilization, but the formation and evolution mechanism of PFRs in biochar are poorly understood because of biochars’ element specificity and chemical structure complexity. In order to further understand the formation and evolution mechanism of PFRs, the PFRs characteristics, chemical structure and element composition of six types of biomasses were investigated. The results revealed that the changing trend of the PFRs types, concentration and line width with pyrolysis temperature is similar for all six feedstocks. The difference in the feedstocks’ properties just affects the absolute value of PFRs’ characteristic parameters. The arrangement and combination of elements and carbon skeleton structure in biochar determine the evolution of PFRs in the pyrolysis process. Additionally, the (H + O)/C atomic ratio of the biomass feedstock and the content of substitutional groups on aromatic rings were found to influence the types of PFRs in biochar. When biochar has a similar O/C atom ratio, a higher H content can reduce the carbon-centered PFRs in biochar. Besides, the reduction in O element content contributes to a decrease in line width due to the reduction in the effect of heteroatoms. The good correlation between O/C atomic ratio, H/C atomic ratio, chemical structure and PFRs characteristics can be used to predict the PFRs characteristics. Combining the changing characteristics in PFRs concentration and carbon skeleton structure of biochar, a three-stage model of PFRs formation and evolution was constructed.
