Tailoring　the　surficial　chemical　environment　of　two-dimensional　materials　by　organic　modification　is　an　effective　way　to　optimize　their　catalytic　behaviors.　Herein,　we　present　a　dynamic　coordination　approach　to　improve　the　photocatalytic　performance　of　ultrathin　Co2CO3(OH)(2)　nanosheets　(u-CoCH)　in　NIR　light　(lambda　＞　780　nm)　driven　carbonylation　reaction　by　using　the　reacting　substrates　(diamines)　as　the　ligands.　The　coordination　of　diamines　with　surface　Co2+　ions　form　a　binuclear　complex　at　the　crystallographic　planes　of　u-CoCH.　The　as-formed　complexes　can　reduce　the　energy　barrier　of　carbonylation　reaction　by　weaking　the　N-H　bond　of　the　substrate　on　u-CoCH,　and　afford　enhanced　light　response　as　well　as　the　prolonged　photogenerated　electron　lifetime.　Together　with　the　successful　synthesis　of　a　series　of　important　structural　motifs　in　pharmaceuticals　and　bioactive　agents,　the　promoted　photosynthesis　reaction　mode　via　in-situ　formed　surface　complexes　offers　a　model　toward　full-spectrum-solar-energy　conversion　in　the　field　of　chemical　synthesis.