N-doped biochar is widely used for activating persulfate to degrade organic pollutants. Which type of N atom is the key factor for activation is still unclear and needs to be further explored and analyzed. In this study, four kinds of biochar were prepared using urea and rice husk as precursors, and tested for the catalytic degradation of dimethomorph. Increasing the nitrogen doping level caused the catalytic removal efficiency of dimethomorph in the presence of peroxymonosulfate increased from 16.6% to 86.8%. A correlation analysis showed that the ability of N-doped biochar to activate PMS is mainly related to the content of pyrrole N, graphite N and carbonyl and the degree of defects. In experiments on electron paramagnetic resonance and free radical suppression, the reactive species of SO4•-, 1O2,·OH and O2.- were detected, among which 1O2 was found to be the main agent in the nonradical pathway. The degradation pathways for dimethomorph were analyzed based on a total of 8 degradation products identified by high-performance liquid chromatography-time of flight mass spectrometry (HPLC-Q-TOFMS). The results of this study provide a fundamental basis for using agricultural waste to produce inexpensive and efficient nonmetal catalysts that are highly effective in reducing dimethomorph levels in agricultural lands.