CeO2 catalyst samples were prepared by the precipitation method using Ce(NO3)(3)center dot 6H(2)O as a precursor. These samples were characterized by N-2 adsorption-desorption, X-ray diffraction, high resolution transmission electron microscopy, and H-2 temperature-programmed reduction. The catalytic performance of these samples for the selective dehydration of 1,4-butanediol to 3-buten-1-ol was investigated. The results show that the CeO2 catalyst samples that were prepared using different precipitants exhibited different morphology. The CeO2 sample precipitated by sodium carbonate showed regular rectangular morphology with clear edges, larger crystallite size, well-grown crystals and preferentially exposed (111) facets. It also had higher activity and higher selectivity in the selective dehydration of 1,4-butanediol to 3-buten-1-ol with yield as high as 59.7%.