Herein, a facile self‐assembly synthesis of magnetic porous ZnFe2O4/MIL‐100(Fe) composites by slowly oxidizing Fe2+ to Fe3+ was reported. By this method, ZnFe2O4/MIL‐100(Fe) composites with a particle size of about 300 nm can be obtained at room temperature and pressure. The efficacy of the products was evaluated for the degradation of Rhodamine B (RhB) under visible light irradiation. It was found that the introduction of MIL‐100(Fe) can not only significantly improve the adsorption capacity of composites and provide more active sites for the degradation process, but also form heterojunctions with ZnFe2O4 particles to efficiently promote separation of photogenerated electron‐hole pairs. Moreover, the existence of ZnFe2O4 provides good magnetic recovery property and photochemical stability to composite samples. These results indicate that ZnFe2O4/MIL‐100(Fe) has obvious application potential in photocatalytic wastewater treatment.