Porous Cu/CeO2 microspheres were synthesized in a system of (NH4)(2)Ce(NO3)(6)/CuSO4-ethanol (EtOH)/H2O-N,N-dimethylformanide (DMF) via a low-temperature hydrothermal route as well as a subsequent calcination. DMF played an important role in both the crystallization of Cu-doped Ce(COOH)(3) precursor and the formation of the precursor microspheres. The size and morphology control of the precursor could be achieved by adjusting the synthesis factors including acidity and temperature. BET measurement indicated that the CuiCeO(2) microspheres possessed pretty high specific surface areas up to 169 m(2) g(-1) and multiple pore systems with the pore diameter of about 1.0 nm, 4.9 nm, and 5.9 nm, respectively. Although the doping content of Cu was pretty low, the copper ions were successfully incorporated into the fluorite structure of CeO2, which made these porous Cu/CeO2 microspheres showing much improved oxygen storage capacity (OSC). The novel porous Cu/CeO2 microspheres might be a promising catalyst for selective CO oxidation. (C) 2014 Elsevier Ltd. All rights reserved.