In wastewater treatment by persulfate-based advanced oxidation processes (PS-AOPs), electron-deficient aromatic pollutants (EDAPs) are refractory to nonradical pathway. To explore an efficient degradation pathway for EDAPs, MgCu-biochar (BC) (x = 0.5, 1, 1.5) activated peroxydisulfate (PDS) was developed, which could trigger reductive species (•H) to reduce EDAPs first, and subsequently facilitate electron-transfer degradation of reduced intermediates. The roles of Mg-doping in MgCu-BC to promote PDS activation and 2,4-dibromophenol (DBP) degradation were investigated. The mechanisms were then explored via electron paramagnetic resonance (EPR), chemical probes and Density Functional Theory (DFT) calculations. The results showed that Mg-doping improved metal-support interactions (MSIs) of MgCu-BC, inducing •H formation via electron transfer from Cu atoms during PDS activation, which was thermodynamically favorable. The degradation rate of DBP (k, 0.0494 min) and Br release (5.35 mg L) in MgCu-BC systems were more 31 and 33 times than that in Cu-BC/PDS system, respectively. The degradation mechanism of •H-enhanced electron transfer processes was that •H attacked one Br group of DBP, and then debrominated intermediates were mineralized by electron transfer processes in the MgCu-BC/PDS system. Overall, this study reports a novel pathway in PS-AOPs for selective degradation of EDAPs in wastewaters.