Dimethyl ether (DME) steam reforming simulating practical applications was tested over catalytic honeycombs coated with ZrO2 and loaded with different amounts of Cu and Zn. The best catalytic performance in terms of activity and yield towards the reforming products, H-2 and CO2, was exhibited by CuZn/ZrO2 with a Cu:Zn molar ratio of 1:10, which also showed high stability. SEM and XPS characterization showed that this catalyst contains very well-dispersed copper particles in contact with ZnO. Catalytic monoliths were also tested in the DME autothermal reforming reaction, but a strong deactivation was observed, probably due to the prevalence of methoxy species that lead to the formation of methane and carbon residues, as evidenced by in situ FTIR and XPS experiments. (C) 2012 Elsevier Ltd. All rights reserved.