In this work, a sludge biochar (CA-SBC-300) with efficient activation of peroxymonosulfate (PMS) was prepared by citric acid modification. CA-SBC-300 achieved efficient degradation of naproxen (NPX) (95.5%) within 10 min by activating PMS. This system was highly resilient to common disruptive factors such as inorganic anions, humic acid (HA) and solution pH. The results of XPS and Raman showed that the content of oxygenated functional groups (OFGs) and the degree of defects on the sludge biochar increased after citric acid modification, which may be an important reason for the enhanced catalytic performance of SBC. In the CA-SBC-300/PMS system, 1O2 and O2•− made the main contributions to the degradation of NPX. XPS analysis and DFT calculations demonstrated that C=O/C−O and pyridine N on CA-SBC-300 were the crucial active sites for PMS activation. According to the results of UPLC-MS analysis, three possible pathways for NPX degradation were inferred. This study provided a feasible strategy for sludge resource utilization combined with efficient catalytic degradation of toxic organic contaminants in wastewater.