Direct synthesis of 1,3-butadiene (BD) from ethanol has been studied using magnesia-silica catalysts doped with transition metal(oxide)s. The effects of Mg/Si ratio, the synthesis procedure, and the dopant concentration were studied. It was demonstrated that modification of the magnesia-silica binary system using a consecutive impregnation step significantly increases the ethanol conversion rate and BD yield. The BD yield higher than 55 mol.% was obtained at full ethanol conversion for materials containing Cu and Ag modifiers. The influence of the reaction temperature and the ethanol concentration in the feed was also investigated. This investigation led to high BD productivity (>0.15 g(BD) g(cat)(-1) h(-1)) and high BD concentration in the product stream (>10,000 Vppm). (C) 2012 Elsevier B.V. All rights reserved.