Creatively constructing Z-scheme composites is a promising and common strategy for designing effective photocatalyst systems. Herein, we synthesized Z-scheme Fe2O3@Ag–ZnO@C heterostructures from the Fe-MOFs and applied it to photodegradation of tetracycline and methylene blue pollutants in wastewater. The optimized sample exhibits a remarkable performance as well as stability under visible light irradiation. The calculating and experimental results demonstrate that the Fe2O3@ZnO nanointerface and carbon sheath together boost the transfer efficiency of photogenerated carriers and absorption ability, thereby improving the photocatalytic activity. Furthermore, detailed mechanism investigation reveals the pivotal role of reactive oxygen species (•OH and •O2–) generated, resulting in remarkable performance. In addition, cell biology experiments reveal that the wastewater after photocatalytic treatment has good biological compatibility, which is important for applications. This work provides valuable information for constructing high-performance Z-scheme photocatalysts from MOFs for environmental treatment.