In this paper, the precursors of the coordination polymer Ce(1,3,5-BTC)(H₂O)₆ with different morphologies have been successfully prepared via a facile and rapid method, and then the CuO/CeO₂ catalysts were obtained by impregnation method to support copper species. The catalysts were characterized by scanning electron microscopy, scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, ultraviolet Raman spectrscopy, N₂ adsorption-desorption, H₂ programmed temperature reduction and X-ray photoelectron spectroscopy, respectively. The results showed that U–CuCeO catalyst has stronger CuO dispersion and higher oxygen vacancy concentration on the surface. The high specific surface area of U–CuCeO catalyst facilitates the highly dispersed CuO species and enhances the interaction between copper and cerium, and improves the catalytic performance compared with the other catalysts. For U–CuCeO catalyst, the CO conversion reached 100% at 120 °C. It also exihibited the broadest complete reaction temperature window.