Herein, a series of Ni/ZrO2 catalysts with tunable ZrO2 crystal phases were synthesized by controlling the calcination temperature of Ni/UiO-66(Zr). Ni/ZrO2-500 (t-ZrO2) exhibited higher activity than Ni/ZrO2-700 (m-ZrO2) in the photothermal Sabatier reaction, which was mainly attributed to a larger concentration of oxygen vacancies on the t-ZrO2 surface.