In this work, we proposed a novel strategy for the photocatalytic degradation of the target pollutants tetracycline (TC) and methylene blue (MB) using core–shell dual metal-organic frameworks (MOFs) composites. A series of mesoporous composites MIL-53@UiO-66 were synthesized by solvent-thermal synthesis via coating UiO-66 on the surface of MIL-53. The results show that under the same degradation conditions, only 30 and 15 min are needed to degrade 93% of TC and 96% of MB in the photo-Fenton reaction system, respectively. The amorphous shell layer brings stronger adsorption to the catalyst. MIL-53@UiO-66 composites with equalizing Fermi level are formed to promote photon absorption and electron transfer. Meanwhile, the MIL-53@UiO-66 composites with excellent stability will be a promising catalyst for environmental remediation.