A series of MgO-SiO2 catalysts were prepared by physical mixture (PM), sol-gel (SG), incipient wetness impregnation (IWI) and wet-kneading (WK) methods. The interaction of ethanol with MgO, SiO2 and as-prepared MgO-SiO2 catalysts surfaces was studied using temperature programmed desorption (TPD) in order to determine the dependence of the reaction pathways on surface acid-base property of these catalysts synthesized by different methods. Dehydrogenation and dehydration reactions occur competitively over the surface of MgO-SiO2 catalysts, depending on the surface acid-base nature of the catalysts. Our results indicated that MgO-SiO2-WK has excellent dehydrogenation ability among these catalysts, which is a critical step in transforming ethanol into 1,3-butadiene (1,3-BD), and those catalysts possessing more acidic sites are more favorable for ethylene formation via ethanol dehydration. The results obtained are also consistent with our previous finding that surface acid-base properties of catalysts is a key factor to determine the reaction pathway as well as the selectivity of cascade transformation of ethanol to 1,3-BD.