Biochar is an economical carbon material for water pollution control, which shows great promise to be applied in the up-scale wastewater remediation processes. Previous studies demonstrate that persistent free radicals (PFRs) on biochar are critical to its reactivity for wastewater remediation. A series of studies have revealed the important roles of PFRs when biochar was applied for organic pollutants degradation as well as the removal of Cr (VI) and As (III) from wastewater. Therefore, this review comprehensively concludes the significance of PFRs for the catalytic capabilities of biochar in advanced oxidation processes (AOPs)-driven organic pollutant removal, and applied in redox processes for Cr (VI) and As (III) remediation. In addition, the mechanisms for PFRs formation during biochar synthesis are discussed. The detection methods are reviewed for the quantification of PFRs on biochar. Future research directions were also proposed on underpinning the knowledge base to forward the applications of biochar in practical real wastewater treatment.