A series of supported gold catalysts have been prepared and tested as a new type of catalyst for the oxidative dehydrogenation of ethylbenzene to styrene. The effects of the supports (alpha-Mn2O3, Fe2O3, TiO2, Al2O3, and CeO2), preparation methods, gold loadings, and reaction conditions have been investigated. Among the catalysts tested, the Au/CeO2 sample containing a 6.0 wt% gold content prepared via a routine deposition-precipitation method exhibited the highest ethylbenzene conversion (66.9%) and remarkable styrene selectivity (91.0%). The superior catalytic performance of the Au/CeO2 catalysts can be attributed to a dramatic increase in the oxygen mobility and storage capacity of the parent CeO2 material in association with the closely contacted Au nanoparticles, which is confirmed by the TPR, total OSC, and XPS measurements.