Dimetoxymethane steam reforming (DMM SR) to hydrogen-rich gas over a bifunctional CuO-CeO2/gamma-Al2O3 catalyst was studied. The performance of gamma-Al2O3, CeO2/gamma-Al2O3, and CuO/gamma-Al2O3 under DMM SR conditions was studied as well to elucidate the role of each catalyst component. BET, TPR, FTIR spectroscopy, XRD, TEM, EDXA and HAADF-STEM techniques were used for catalyst characterization. Complete DMM conversion was observed over the CuO-CeO2/-gamma-Al2O3 catalyst under atmospheric pressure, T= 300 degrees C, GHSV= 10,000 h(-1) and H2O/DMM = 5 mol/mol with hydrogen productivity of 15.5 L H-2/(g(cat).h) and CO content in the hydrogen-rich gas below the equilibrium value. DMM SR proceeds via a consecutive two-step reaction mechanism including DMM hydration to methanol and formaldehyde on gamma-Al2O3 acid sites and steam reforming of the formed methanol and formaldehyde to hydrogen-rich gas on alumina-supported mixed copper-cerium oxide species. The CuO-CeO2/-gamma-Al2O3 catalyst proved to be highly-promising for multi-fuel processor approach: steam reforming of DMM, dimethyl ether and methanol on the same catalyst under similar reaction conditions to hydrogen-rich gas for fuel cell feeding. (C) 2014 Elsevier B.V. All rights reserved.