The efficient and straightforward treatment of organic contaminants in water remains a significant challenge. This study presents the synthesis of a defective NH2-MIL-88Fex/Cuy photo-Fenton catalyst via a simple one-pot hydrothermal method. The incorporation of the inexpensive metal Cu enhances the valence cycles of Cu2+/Cu+ and Fe3+/Fe2+ under the photo-Fenton system, thereby compensating for the rapid consumption rate of ·OH radicals. Degradation tests demonstrated that NH2-MIL-88Fe0.5/Cu0.5 can degrade 99.99 % of methylene blue within 30 min under visible light irradiation. Free radical trapping experiments and Electron Paramagnetic Resonance (EPR) confirmed that ·OH radicals play a predominant role in the catalytic system. Density Functional Theory (DFT) calculations verified the improved binding energy of the catalyst materials following the introduction of structural defects. The degradation pathway and mechanism of methylene blue were elucidated. This study offers a novel approach for designing photo-Fenton catalysts and holds significant promise for practical applications in wastewater treatment.