In this work, a new preparation method is developed for the preparation of Ce/Ni-ZrO2 nano-catalyst (Ce/Ni-ZrO2-N). Although scholars have studied similar catalytic systems, there is still room for improvement in terms of nickel surface area, catalytic efficiency, and mechanism analysis. The Ce/Ni-ZrO2-N exhibits a large nickel surface area (50.6 m2∙g-1) and a small nickel particle size (~5.1 nm), which uses UiO-66 not only as a precursor for the preparation of ZrO2 with a large surface area, but also as a dispersant for the confinement of nickel nanoparticles. The catalyst demonstrated excellent catalytic performance at high GHSVs. With a 16-fold increase in GHSVs, the CO2 conversion of Ce/Ni-ZrO2-N decreased by only 32.1%, while that of the control group is 50.3%. This is attributed to the high nickel surface area and relatively low activation energy. Moreover, the characterization and Density Functional Theory (DFT) studies revealed that electron transfer from Ce to Ni enhances the activation of CO2 on the Ni sites, which subsequently contributes to a better catalytic performance. In addition, the catalyst showed excellent anti-coking ability during the 40 h's testing, which, according to DFT calculations, is attributed to the high energy barrier for coke formation on the active sites.