The Fenton-like reaction is one of the most effective methods for decomposing organic pollutants in water. Designing efficient heterogeneous catalysts is crucial in this industry. The hard template method was used to construct FeCeOx materials with Fe-doped ordered mesoporous structures, and the impregnation method was employed to create multi-metallic active sites after loading Cu and Co as the carrier. Methylene blue could be entirely eliminated in 45 min by using an as-prepared catalyst with strong recycling capacity. After 5 runs, methylene blue degradation could still reach 93.3%. The porous structure of the catalyst is conducive to enhancing methylene blue absorption, exposing more active spots, and the synergistic effects of multi-metals promote electron transport, thus boosting the activation efficiency of H2O2 and the formation of ·OH.