A series of acid-base bifunctional CaO-ZrO2 catalysts was prepared simply by the impregnation method and evaluated for the vapour-phase dehydration of 1,4-butanediol (BDO). The effects of CaO content and calcination temperature on the catalytic properties of the CaO-ZrO2 catalysts were investigated. It was found that the catalyst with 12.5 wt% CaO and at a calcination temperature of 650 C exhibited favorable catalytic performance and good stability for the selective dehydration of BDO to 3-buten-1 -ol (BTO). The maximum BTO selectivity and BDO conversion reached 68.9% and 94.6%, respectively. The formation of by-product, THF, was markedly suppressed. These catalysts were characterized by N-2 physisorption, XRD, FT-IR spectra, NH3-TPD and CO2-TPD. The results indicated that the CaO-ZrO2 catalysts showed higher basicity density and similar acidity density compared to unmodified ZrO2 due to the formation of Ca-O-Zr Hetero-linkage by CaO introduction. The catalytic performance depended on the coexistence of acidic and basic sites on the surface of catalysts. (C) 2013 Published by Elsevier B.V.