One-step CO2 hydrogenation reaction to dimethyl ether (DME) on a bifunctional system constituted by Cu-ZnO-ZrO2 (ZCZ) methanol synthesis catalyst and HZSM-5 zeolite was studied. The influence of the reactor configuration in terms of combination procedure of the admixed samples on activity, selectivity and DME yield has been evaluated. The results obtained at T-R = 513K, P-R = 3.0 MPa and GHSV = 9000 NL g(cat)(-1) h(-1) show a superior DME productivity (4.4 mmol kg(ZCZ)(-1) s(-1)) using the bifunctional catalyst prepared by physical mixing. A combined effect of active sites located at metal/oxide(s)-acid interface was claimed as the main factor affecting the CO2 conversion and DME productivity. The strong surface acidity of ZCZ catalyst is not suitable to drive DME synthesis through a consecutive mechanism, while DME formation effectively proceeds on weak and medium acid sites of HZSM-5. (C) 2013 Elsevier B.V. All rights reserved.