Hybrid materials based on metal-organic frameworks (MOFs) and nanoparticles (NPs) have gained considerable popularity in a variety of applications. Particularly, these types of materials have demonstrated excellent efficiency in heterogeneous catalysis due to the synergistic effect between the components. Herein, we report a simple, eco-friendly, photocatalytic method for the fabrication of Zr containing MOF-801 and a silver (Ag) NPs-based hybrid (Ag@MOF-801). In this method, the photocatalytic property of the central metal ion (Zr) of MOF was exploited to promote the formation and deposition of Ag NPs on the surface of the MOF-801 under the irradiation of visible light. The successful incorporation of Ag NPs was ascertained by powder X-ray diffraction (XRD) and UV-Vis analysis, while the morphology and surface area of the sample was determined by N2 adsorption–desorption and scanning electron microscopy (SEM), respectively. The resulting Ag@MOF-801 hybrid served as a highly efficient catalyst for the transesterification of used vegetable oil (UVO) for the production of biodiesel. The Ag@MOF-801 catalyst exhibited superior catalytic activity compared to its pristine MOF-801 counterpart due to the enhanced surface area of the material.