Morphological control can be used to improve the catalytic activity of cerium oxide (ceria, CeO2). In this study, ceria with a high specific surface area was synthesized via the hydrothermal reaction of ceric nitrate and was tested for the catalytic conversion of ethanol to ethylene. As a reference, ceria was also synthesized via a precipitation reaction of cerous nitrate using aqueous ammonia. The Japan reference catalyst JRC-CEO-1 also served as a reference. The specific surface area of the hydrothermally synthesized ceria was as high as that of JRC-CEO-1, but was much higher than that of either reference after calcination at 873 K. Thermogravimetric analysis and IR spectroscopy revealed that the cerias made by hydrothermal and precipitation reactions consisted of high-purity CeO2, whereas JRC-CEO-1 contained 1.5% decomposable functional groups (OH-, CO32-). For both ethanol conversion and ethylene selectivity in a catalytic dehydration reaction of ethanol, the activity of the hydrothermally developed ceria was higher than that for either reference. The reaction pathway for the dehydration reaction of ethanol over ceria showed that the specific surface area and the basicity of the Lewis basic sites of the ceria were influential properties. The high catalytic activity of the hydrothermally synthesized ceria was derived from its high specific surface area and high-purity CeO2.