Ni supported on the ordered mesoporous CexZr1−xO2 with various Ce/Zr molar ratios prepared by a programmed evaporation-induced self-assembly method were employed for dry reforming of methane. The systematical techniques, including X-ray diffraction, N2 physisorption, Raman, transmission electron microscope, chemisorption, X-ray photoelectron spectroscopy, diffuse reflection Fourier transform infrared spectrum, thermogravimetric analysis, etc. were used to clarify the structure-activity relationship. It was found that the prepared catalysts all had highly ordered mesoporous structures, and compared to the sole ZrO2 and CeO2, the CeO2-ZrO2 composites exhibited the best thermal stability, stronger basicity, and greater oxygen migration. Especially, the composite with Ce/Zr ratio of 1/4 possessed the suitable basicity and most oxygen vacancies, which were closely related to the excellent anti-carbon ability. Moreover, its supported catalyst had the strongest metal-support interaction and highest Ni dispersion. Expectedly, the catalyst showed the superior activity and the robust stability for at least 1800 min