A series of Ca-doped Ni/La2Zr2O7 catalysts were prepared by co-precipitation method. The obtained composite metal oxides with high stability of the pyrochlore structure were investigated as the catalysts for the carbon dioxide reforming of methane. The structure, morphology, reduction performance and carbon deposition of the catalyst were studied by XRD, BET, TEM, H-2-TPR and TG-DSC. The results showed that all catalysts typically exhibited a pyrochlore structure. The crystallinity of the samples with calcium doping was somewhat reduced compared to that without. The increase of specific surface area, pore volume and the existence of its mesoporous structure promoted the dispersion of the active component Ni, which showed good catalytic performance in the methane reforming reaction. Among them, NLZCa6, a catalyst with Ca doping content of 6%, showed excellent methane reforming catalytic performance. Its CH4 conversion and CO2 conversion rates reached 85% and 92% at 750 degrees C. During the 35-h activity evaluation period, the catalyst showed high stability.