In this work, we designed a hybrid catalyst composed of a metal–organic framework (MOF), Pt nanoparticles (NPs), and ferric oxide, namely, Co-MOF-74@(Pt@Fe2O3), which enables not only high turnover frequencies of up to 245.7 h–1 but also ultrahigh 100% selectivity toward cinnamyl alcohol in the hydrogenation of cinnamaldehyde under mild conditions. This excellent performance is attributed to the fact that such a hybrid catalyst enables not only strong steric constraint to provide the favored CO adsorption of cinnamaldehyde but also strong metal–support interaction to lower the electron density of Pt NPs.