The addition of basic solutions to the reaction medium in the catalytic hydrogenation of styrene oxide improves the selectivity to 2-phenylethanol (used in perfumery) but also can favour condensation reactions. To study the influence of different basic sites on the reaction products, we prepared several catalysts by mixing a commercial magnesia (MgO), and other previously rehydrated (MgOr), with different amounts of NiO followed by reduction (NiMgO, 4NiMgO, NiMgOr, 4NiMgOr), and by mixing directly MgO with Ni (NiMgOa, 4NiMgOa). Ni-MgO catalysts showed the best conversion and selectivity to 2-phenylethanol values, arriving to 100% when increasing the MgO content. Interestingly, CO2-TPD study of catalyst NiMgO indicates that metallic nickel covers the weakest basic sites of magnesia. On the other hand, CO2-TPD profiles of Ni-MgOr and Ni-MgOa catalysts, which present low catalytic activity, showed an important amount of available basic sites that favour the formation of higher amounts of condensation products, which are responsible for the catalyst deactivation.