Regulating　charge　transfer　and　reaction　pathways　are　effective　strategies　for　boosting　photocatalytic　CO2　reduction.　Herein,　Co3O4/ZrO2　mesoporous　octahedrons　are　synthesized　through　facile　pyrolysis　of　UIO-66@ZIF-67　core/shell　octahedrons.　The　as-obtained　Co3O4/ZrO2　mesoporous　octahedrons　are　assembled　by　highly　dispersive　and　small-sized　nanoparticles,　with　13　nm　average　particle　size　and　5.8　nm　pore　width,　leading　to　a　high　specific　surface　area　of　43.11　m2　g−1.　Benefiting　from　active-site　engineering,　the　charge-transfer　kinetics　and　CO2　adsorption　are　successfully　enhanced.　In　addition,　density　functional　theory　calculations　reveal　that　ZrO2　tailors　the　reaction　pathway　of　CO2　reduction　by　promoting　CO2　activation　to　*CO2　and　intermediate　formation　(*COOH　and　*CO),　as　well　as　decreasing　the　energy　barrier　of　the　rate-limiting　step　(*CO→CO).　Thus,　the　Co3O4/ZrO2　mesoporous　octahedrons　afford　a　turnover　frequency　of　28.82　h−1,　16.95-fold　larger　than　pure　Co3O4.　©　Science　China　Press　2024.