In this study, a novel bimetallic complexation-curing nucleation-anaerobic calcination method was developed to synthesize a nano-CuFe2O4@coconut shell biochar (CuFe2O4@CSBC) catalyst to activate peroxymonosulfate for degradation of tetrabromobisphenol A (TBBPA). The reaction processes of the TBBPA on CuFe2O4@CSBC have been investigated using in situ characterization and metal leaching. The effects of initial reaction conditions and degradation mechanism were investigated. Greater than 99% degradation of TBBPA at 10 mg L-1 was achieved in 30 min under the condition of pH 11, a total organic carbon removal rate of up to 70.67% was achieved and the degradation efficiency was 90% after 5 cycles of CuFe2O4@CSBC use. The degradation was in a second-order reaction at a constant of 0.797 M-1 min-1 (R2 = 0.993). The degradation was attributed to the main active species (SO4·-≈·OH < 1O2), and the surface active site of CuFe2O4@CSBC was the key role. The degradation process involved three main degradation pathways. Path A: ·OH attacked the C-Br bonds (TBBPA→TriBBPA→DBBPA→MBBPA→BPA); Path B: Hydroxylation and decarboxylation; Path C: Dehydrocoupling of TBBPA. What's more, the practical application of the system was very positive, achieved >77% degradation in sewage and industrial wastewater.