CeO2(rod) has been found to be exposed four {111} planes and two {100} planes with a hexangular cross section, and the growth mechanism follows to the oriented attachment of the cube-like basic grains with a [110] growth direction and the subsequent Ostwald ripening, corresponding to the increasing lateral size and longitudinal size with prolonging the hydrothermal time. Equal amount of copper oxide totally highly distributed on the surface of CeO2(rod) supports with different abundance of oxygen vacancies facilitate to produce the strongly bound Cu-[O-x]-Ce species to different degrees (supported by XPS, H-2-TPR and in situ DRIFTs results), which is encouraged by prolongation of hydrothermal time of CeO2(rod) supports. The essential role of interfacial Cu-Ce interaction in CuCe(rod) catalysts for CO-PROX was identified by the enhanced catalytic performance of CuCe(rod)-48h, on account of much stronger Cu-Ce interaction generated in it. Moreover, we proposed a potential structural model of strongly bound Cu-[O-x]-Ce to interpret the synergetic effect of copper and ceria species in CuO/CeO2 catalysts and generalized the possible reaction mechanism for CO-PROX over the CuCe(rod) catalyst. (C) 2017 Elsevier B.V. All rights reserved.