Biochar works as the catalyst for activating peroxymonosulfate (PMS) to produce highly oxidizing radicals to remove organic contaminants from wastewater, but its activity requires further improvement. Recent research demonstrates that the PMS activation performance of biochar is closely related to the oxygen-containing functional groups (OFGs). Therefore, biochar/montmorillonite (BC/Mt) composites are designed for activating PMS toward degrading tetracycline. The negative charge of Mt. induced the electron transfer form Mt. to BC, which increases the nucleophilicity of C–O groups that promote the activation of PMS to center dot OH and SO4 center dot- radicals. Meanwhile, the pyrolysis path of rice straw is tuned by Mt., and the amount of COO groups is increased from 8.99% to 9.79% that promotes the generation of 1O2. Moreover, electron paramagnetic resonance and quenching experiments reveal that the activation mechanism of PMS by the BC/Mt. is comprised of both the radical and the non-radical pathway. Consequently, the tetracycline degradation kinetics using the optimized BC/Mt. (0.117 min-1) is higher than either bare BC (0.0866 min-1) or bare Mt. (0.0258 min-1), highlighting the significance of the rational design of electrocatalysts toward the enhanced catalytic chemistry. This work provides a facile route to improve the catalytic performance of biochar by hybridizing with clay minerals and is of great significance to promote the practical application of PMS-based advanced oxidation processes.