The oxygen-containing functional groups of biochar have great potential in tailoring photochemical properties, but the content of oxygen-containing functional groups of pristine biochar is insufficient to support photocatalytic reactions. In this study, a synergistic oxidation of H2SO4 and H2O2 was innovatively proposed to prepare biochar photocatalysts (OGPC400). The results showed that the synergistic oxidation of H2SO4 and H2O2 increased the contents of hydroxyl and carboxyl groups of biochar with the degree of oxidation, and the total concentration of acidic functional groups was about 4 mmol/g higher than that of the oxidation with H2SO4 or H2O2 alone, which was attributed to the synergistic oxidation to promote the conversion of CH and C-OH on the benzene ring. The achievement of electron exchange among hydroxyl and carboxyl groups and internal electron transfer within biochar by the benzene ring as a medium resulted in 100 % degradation of rhodamine b (RhB) and 25 times reaction rate constant higher than that of pristine biochar, as compared to only 45 % or 37 % degradation by oxidation with H2SO4 or H2O2 alone. The exciting results confirmed the positive availability of H2SO4 and H2O2 synergistic oxidation on biochar photocatalysts, which is expected to be applied in environmental remediation.