Au-CeO2 catalysts are prepared from amorphous Ce-Al alloys by the dealloying method, and their catalytic performances are examined in the oxidation of benzyl alcohol to benzaldehyde using O-2 as an oxidant. The catalytic activity of the Au-CeO2 catalysts is improved using an amorphous alloy as a precursor, and further improved activity is attained by directly alloying Au with Ce-Al rather than by depositing Au on preformed CeO2. Consequently, Au-CeO2 prepared directly from an amorphous Au Ce-Al alloy exhibits the highest activity among the prepared samples, despite its low surface area. Detailed characterization by means of XPS analysis indicates that most of the Au species in Au-CeO2 prepared from the amorphous Au Ce-Al alloy exist in a +1 oxidation state (Au+). The presence of Au+ facilitates the migration of oxygen atoms through the lattice, which likely contributes to the high catalytic activity of the Au-CeO2 catalyst.