Abstract:　Photocatalytic　reduction　of　CO2　to　useful　fuel　has　been　identified　as　a　promising　strategy　to　address　the　energy　and　environmental　issues.　Development　of　well-defined　photocatalysts　toward　CO2　reduction　has　attracted　increasing　interest　to　gain　insight　into　the　reactive　mechanism.　Herein,　by　post-synthetic　ligand　exchange,　a　bifunctional　Re-based　metal–organic　framework　(MOF)　was　successfully　prepared.　It　not　only　serves　as　a　photosensitizer　but　also　acts　as　a　catalyst　for　photochemical　reduction　of　CO2.　Furthermore,　it　is　found　that　a　Re-based　MOF　containing　30%　Re-based　ligands　displays　improved　activity　compared　to　MOF　with　100%　Re-based　ligands.　This　work　provides　clues　to　the　design　and　synthesis　of　bifunctional　MOFs　toward　photocatalytic　CO2　reduction.　Graphical　abstract:　A　bifunctional　UiO-67-Re　was　developed　as　a　photocatalyst　for　CO2　reduction　by　post-synthetic　ligand　exchange　strategy.　Its　synthesis　and　photocatalytic　performance　were　investigated.[Figure　not　available:　see　fulltext.].　©　2019,　The　Nonferrous　Metals　Society　of　China　and　Springer-Verlag　GmbH　Germany,　part　of　Springer　Nature.