he photocatalytic reduction of CO₂ to CO is considered one of the potential methods to meet the increasing energy demand and greenhouse gas emissions. However, some issues, such as light harvesting, recombination of the electron–hole pairs, and catalytic selectivity, limit the photocatalytic performances. In this study, a ruthenium complex RuL₂L′ (L = bpy, L′ = dcbpy) sensitizing g-C₃N₄/MOF hybrid (RuL₂L′@C₃N₄/MOF) was exploited for the photocatalytic reduction of CO₂ to CO. The synergies between components have greatly improved photocatalytic performances. Within 3 h of irradiation, 4688 μmol g⁻¹ of CO and 727 μmol g⁻¹ of H₂ were detected, and the selectivity of CO was up to 86.6%. This meaningful study provides a new opportunity for developing efficient photocatalysts.