In this paper, copper-doped ceria oxides with different hollowness and size are fabricated by changing the Cu(2+) doping concentration in the mixed water-glycol system. Results show that the copper-doped CeO₂ oxides undergo a morphology transformation from the solid nanospheres to core-shell, then to hollow nanospheres with the increase of the Cu(2+) doping concentration. The corresponding size becomes smaller during this transfer process. The Cu(2+) doping induced acceleration in the nucleation and growth process is further investigated. The resultant Cu(2+)-doped CeO2 oxides exhibit enhanced CO conversion performance and better reduction behaviors.