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Mesoporous heterojunction MOF-derived α-Fe2O3/ZnO composites were prepared by a simple calcination of α-Fe2O3/ZIF-8 as a sacrificial template. The optical properties confirm that coupling of both the modified pore and the n–n heterojunction effectively reduces the possibility of photoinduced charge carrier recombination under irradiation. The mesoporous Fe(25)ZnO with 25% loading of α-Fe2O3 exhibited the best performance in MB degradation, up to ∼100% after 150 minutes irradiation, higher than that of pristine ZnO and α-Fe2O3. Furthermore, after three cycles reusability, mesoporous Fe(25)ZnO still showed an excellent stability performance of up to 95.42% for degradation of MB. The proposed photocatalytic mechanism of mesoporous Fe(25)ZnO for the degradation of MB corresponds to the n–n heterojunction system. This study provides a valuable reference for preparing mesoporous MOF-derived …