Core/shell nanostructures of polystyrene (PS)/CeO2 have been prepared on conductive glass substrates by using a novel electrochemical route consisting of (i) the electrophoretic deposition of a PS sphere monolayer on the substrate and (ii) the following potentiostatic electrodeposition of CeO2 on the PS sphere template in Ce(NO3)3 aqueous solutions. The structural morphologies of the deposit changed drastically depending on the Ce(NO3)3 concentration; i.e., spherical and needlelike shells were deposited. The deposit was formed only on the PS sphere surface because of an interaction between cationic cerium species and a sulfate group that was immobilized on the PS sphere surface. The spherical shell layer was assigned as CeO2, and the needlelike shells were composed of Ce(OH)3 needles formed on the CeO2 layer surface, indicating that the deposit species changes from CeO2 to Ce(OH)3 during electrodeposition only in a 1 mM Ce3+ solution. Deposition of Ce(OH)3 would begin when electrogenerated hydrogen peroxide was consumed by decomposition under reductive conditions and could no longer oxidize Ce3+ ions. The corresponding CeO2 hollow shells were obtained by thermal elimination of the PS sphere core and transformation of Ce(OH)3 into CeO2 while keeping their original shapes.