Interfacial electron transport and reactive oxygen species (ROS) generation in the redox action between biochar (BC) and low-molecular-weight organic acids (LMWOAs) have been overlooked during the utilization of BC in soil amelioration/remediation. Herein, BC and N-doped BC (NBC) with various physicochemical properties were prepared at pyrolysis temperatures of 350, 550 and 750 degrees C (namely BC/NBC350, 550 and 750) and their in-teractions with LMWOAs were systematically investigated. Results of ROS quenching and electrochemical cell experiments revealed that BC/NBC could strongly interact with LMWOAs, especially ascorbic acid (AA), and acted as an electron shuttle to mediate one electron transfer from AA to oxygen to generate O-2(center dot-), followed by the robust generation of H2O2 and center dot OH. Interestingly, the generation rates of center dot OH and H2O2 in the NBC-AA system were significantly higher than that in the BC-AA system, of which the NBC550-AA system exhibited the best performance, enabling its superior ability in bisphenol A degradation. Different from conventional wisdom, the electron shuttle capacity depended on a combined aromatization degree and electron-accepting capacity of BC/ NBC. These findings complement the interfacial electron transfer mechanism during the natural BC-LMWOAs interaction and provide new inspiration for the development of green and efficient organic pollutant removal technologies.