Three different CeO2 sphere nanomaterials (hollow sphere, flowerlike sphere, spherical cluster) were controllably synthesized by carbon sphere template method, hydrothermal and solvothermal method respectively. Then 2.5 wt% Au was doped on the supports by the deposition precipitation method and Au/CeO2 catalysts with three different morphologies were obtained. Composition, morphology and structure of these catalysts were characterized by the techniques of XRD, Raman, TPR, SEM and TEM, and the activity for CO oxidation of the catalysts was investigated. The catalytic test results indicated that the addition of Au could remarkably improve catalytic performance on CO oxidation. The activities of the three catalysts differ largely, the flowerlike Au/CeO2 catalyst had the highest activity for CO oxidation and its T100% was 29°C. The mechanism for the different activity of the catalysts was investigated. H2-TPR result indicated flowerlike had a more intensive peak at 125°C than others and it implied more reducible Au species in this case, that plays a vital role in the CO oxidation.