Mixed zinc, titanium and alumina oxides were characterized by X-ray diffraction (XRD) and TPD-methanol techniques. The surface properties were correlated with the products from methanol decomposition. XRD results showed that 20% of ZnO supported on Al 2O 3 and on TiO 2/Al 2O 3 formed zinc aluminate phase. However, 20%ZnO/TiO 2 and 20%TiO 2/Al 2O 3 presented the characteristic structure of the oxides as segregated phases. TPD-methanol results for 20%TiO 2/Al 2O 3 sample showed an intense CO desorption, which was associated with a large density of Lewis acid sites due to TiO 2 surface and to the Lewis and Brönsted acid sites of alumina. On the other samples, the higher density of basic sites and weak Lewis acid site was related to ZnO presence that increased the CO 2 desorption. The high H 2/CO 2 ratio and the absence of CO and other desorption products showed that ZnO/TiO 2 is a promising system to be used as support or catalyst to H 2 production employed in fuel cells.