The synthesis of highly dispersed metal nanoparticles supported on metal-organic frameworks has been widely studied as a means to provide high-performance heterogeneous catalysts. Here, a Ru-nanoparticles-supported MIL-101(Cr) catalyst was prepared via a diamine and oxo-centered trimeric ruthenium cluster ([Ru-3(mu(3)-O)(mu-CH3COO)(6)(H2O)(3)]CH3COO), Ru-3 cluster sequential grafting, followed by alcohol reduction. Ethylenediamine (ED) acted as the linker, coordinating with unsaturated sites on both MIL-101(Cr) and the Ru-3 cluster to produce Ru-3-ED-MIL-101(Cr), after which selective alcohol reduction process provided the Ru/ED-MIL-101(Cr) catalyst. The synthesized Ru/ED-MIL-101(Cr) catalyst contained small, finely dispersed Ru nanoparticles, and the structural integrity of ED-MIL-101(Cr) was maintained. The Ru/ED-MIL-101(Cr) catalyst was tested for the transfer hydrogenation of benzene using isopropanol as the hydrogen source, where it was shown to outperform other Ru-based catalysts.