3D porous CeO₂ with various morphologies was successfully synthesized via a facile precipitation using glycine as the soft bio-template. During the synthesis, it was demonstrated that the morphology of CeO₂ depended on the molar ratio of reactants. Furthermore, the catalytic performance towards CO oxidation of the as-synthesized CeO₂ with different morphologies was investigated. CeO₂ with a bowknot shape showed excellent catalytic performance, giving complete CO conversion at 370 °C, due to its properties of much higher oxygen vacancies, loosely packed pore structure and larger specific surface area.