Using heterobimetallic metal-organic frameworks (MOFs) as the precursor, a series of inverse CeO2/CuO catalysts, by which cerial nanoparticles were patched on a copper oxide support, were synthesized. These catalysts exhibited excellent catalytic activity and selectivity during preferential CO oxidation in the H-2-rich stream. This new approach based on MOFs precursor has two advantages for optimizing the inverse CeO2/CuO catalysts with more copper-ceria interfacial sites: 1) the highly ordered metal-oxygen clusters were completely separated by the organic linkers; and 2) the Ce/Cu configuration can be modulated. We further found that the calcination temperature and heating rate of MOFs are critical for their catalytic activity. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.