Proposed to prepare phosphorus-doped biochar catalyst materials by impregnation pyrolysis method using corn stover and different phosphorus source precursors as raw materials, and the batch-wise research revealed that the phosphorus source precursor, the doping ratio, and the pyrolysis temperature had a significant influence on the biochar properties. The biochar material Pb-C-4–600 prepared with (C4H9)3PO4 as phosphorus source precursor, 1:4 doping ratio, and pyrolysis temperature of 600 ℃ had an ID/IG = 0.914, pore size of 4.91 nm, and specific surface area of 173.9845 m²/g, which was 93.4 times higher than that of the pure biochar. The removal rate of TCH reached 99.77 % in 30 min under the reaction conditions of PMS concentration of 2 g/L, Pb-C-4–600 dosage of 1 g/L, and pH 3. Comparing the efficacy of Pb-C-4–600 and different catalysts for the degradation of TCH by activated PMS under the same reaction conditions, the degradation reaction rate of Pb-C-4–600 was 0.17663 min−1, which was 1.48 times higher than that of N-bio, 1.67 times higher than that of S-bio, and 2.64 times higher than that of B-bio, which further demonstrating the advantages of Pb-C-4–600 in similar composites. The oxidative degradation performance of other typical organic pollutants (BPA, phenol, AO7) was also good. The prominent reactive oxidizing radical in the system of Pb-C-4–600/PMS was SO4·−, and the system could adapt to a wide pH range.