Photoreduction　of　CO2　to　useful　ingredients　remains　a　great　challenge　due　to　the　high　energy　barrier　of　CO2　activation　and　poor　product　selectivity.　Herein,　Polyvinyl　pyrrolidone　(PVP)　coordinated　BiOBr　was　synthesized　by　a　facile　chemical　precipitation　method　at　room　temperature.　The　CO2　photoreduction　behaviors　of　PVP　coordinated　BiOBr　were　evaluated　with　H2O　without　sacrificial　agent　under　the　simulated　sunlight.　The　evolution　rates　of　CO　and　CH4　are　263.2　µmol　g−1h−1　and　3.3　µmol　g−1h−1,　which　are　8　times　and　2　times　higher　than　those　of　pure　BiOBr　respectively.　Furthermore,　the　coordination　of　PVP　on　BiOBr　surface　enhances　greatly　the　selectivity　of　product　CO,　which　is　close　to　100%.　Loading　PVP　onto　BiOBr　could　not　only　induce　and　stabilize　the　oxygen　vacancy,　but　also　increase　the　charge　density　of　BiOBr　via　the　ligand　to　metal　charge　transfer　(LMCT),　which　could　be　beneficial　to　the　adsorption　and　activation　of　CO2　molecule.　The　photoreduction　mechanism　of　CO2　for　PVP　coordinated　BiOBr　was　proposed　based　on　the　improved　charge　density　of　BiOBr　by　the　experimental　results　and　Density　functional　theory　(DFT)　calculations.　This　finding　provides　a　new　pathway　to　boost　the　conversion　efficiency　and　selectivity　for　the　activation　of　CO2　photoreduction　and　new　molecule　insights　into　the　role　of　PVP　in　photocatalysis.　©　2021　Elsevier　Inc.