Metal–organic frameworks (MOFs) have been extensively used for catalytic reactions due to their abundant structures, regular reticulated channels, and high specific surface areas. They are good platforms for the fabrication of various composites, including metals, oxides, or carbides. Therefore, MOFs can be used as templates to fabricate heterostructures with excellent photocatalytic performance. In this study, the defective ordered macroporous Zeolitic Imidazolate Framework–8/ZnO (D–OM–ZIF–8/ZnO) heterostructure is constructed through the in situ conversion of ordered macroporous ZIF–8 (OM–ZIF–8). The introduction of self–defects into OM–ZIF–8 results in a wide visible–light response band. The ZnO nanoparticles that have formed on the surface of OM–ZIF–8 can effectively regulate surfaces and interfacial states and then construct the heterostructure. The ordered macroporous structure shows considerable advantages for improving carrier mobility, mass transfer rate, and light utilization during photocatalysis. D–OM–ZIF–8/ZnO demonstrates remarkable photocatalytic degradation activity for tetracycline and methylene blue under visible–light. Therefore, our novel construction strategy opens a door for designing ordered microporous MOF–based heterostructures as potential visible–light photocatalysts.