In this study, we investigated the ability of a magnetic wood biochar (WB)-based composite catalyst (Fe3O4–WB) to catalyze sodium persulfate (PS) for the remediation of estuary sediment contaminated with polycyclic aromatic hydrocarbons (PAHs). The effects of various critical parameters, including the catalyst dose and initial pH, were investigated. The degradation of the PAHs was found to be related to the number of rings in their structure. The results showed that Fe3O4–WB is an efficient catalyst for the removal of high-ring PAHs (HPAHs), with the highest degradation rates for the 6-, 5-, and 4-ringed PAHs being 90%, 84%, and 87%, respectively, for a PS concentration of 2 × 10−5 M, catalyst concentration of 3.33 g/L, and pH of 3.0. That the reduction rate of the HPAHs was greater than that of the low-ring PAHs can be attributed to the strong affinity of the HPAHs for biochar derived from wood biomass. Overall, this study revealed that the WB-mediated electron transfer catalysis of the surface functional groups in a wide range of pH in the Fe3O4–WB/PS system and potentially application in the remediation of sediments contaminated with PAHs.