Recent developments have been highlighted for UiO-type materials, a class of metal-organic frameworks (MOFs) with high stability, as catalysts for photocatalytic CO2 reduction. We design and synthesize two metal ion (Co2+, Re+)-doped UiO-67 as catalysts for the photocatalytic CO2 reduction reaction and demonstrate that Co-UiO-67 exhibits better photocatalytic activity relative to Re-UiO-67. The superior photocatalytic activity of Co-UiO-67 over Re-UiO-67 results from the improved charge transportability and higher CO2 adsorption capacity. Density functional theory (DFT) calculations reveal that the energy barrier of Co-UiO-67 (0.86 eV) for catalytic CO2 reduction to CO is lower than that of Re-UiO-67 (0.92 eV), thus leading to superior photocatalytic performance of Co-UiO-67 than that of Re-UiO-67.