Framework Cu doped Al2O3 dispersed on KIT-6 (Cu-Al/KIT-6) was synthesized by the ultrasonic impregnation method and characterized by multi-technologies. The catalyst performed superior catalytic performance and stability for bisphenol A (BPA) degradation in heterogeneous Fenton-like catalysis. Especially, the effect of O2 and N2 on BPA degradation was detected over Cu-Al/KIT-6 in the presence of hydrogen peroxide (H2O2). DMPO spin-trap electron spin resonance (ESR) experiments indicated that O2 can be activated to produce reactive oxygen species (ROS) by Cu(I) on the surface of Cu-Al/KIT-6. Meanwhile, O2 as an electron acceptor can trigger the reaction at the beginning of reaction, which decreased the consumption of H2O2. In addition, BPA and its intermediate products chelate with Cu(II) to form Cu(II)-phenol complex, resulting in a series of reactions to further promote BPA degradation. These findings provide useful insights into the fundamental theories of Fenton catalysts via interface engineering for practical application.