Herein, we developed a one-pot tandem catalytic process for the hydrogenation of dimethyl terephthalate (DMT) to 1,4-cyclohexanedimethanol (CHDM) with physically mixed 5 Pd/CMK-3 and Cu-600 catalysts in a batch reactor. The reaction process was systematically studied in order to improve the yield of CHDM. The hydrogenation of the phenyl group of DMT was preferential to the ester groups, mainly owing to strong adsorption of DMT and the high activity of the 5 Pd/CMK-3 catalyst, as confirmed by UV–visible spectra and kinetic studies. Up to 82% yield of CHDM can be achieved under the optimized reaction conditions. The possible reaction pathways were proposed based on the detailed investigations with different reactants and catalysts. Promisingly, the developed method may lay a solid foundation for the one-pot synthesis of CHDM via the hydrogenation of DMT.