High　carrier　separation　efficiency　and　rapid　surface　catalytic　reaction　are　crucial　for　enhancing　catalytic　CO2　photoreduction　reaction.　Herein,　integrated　surface　decoration　strategy　with　oxygen　vacancies　(Ov)　and　anchoring　CuxO　(1　＜　x　＜　2)　nanodots　below　10 nm　is　realized　on　Bi2MoO6　for　promoting　CO2　photoreduction　performance.　The　charge　interaction　between　Ov　and　anchored　CuxO　enables　the　formation　of　enhanced　internal　electric　field,　which　provides　a　strong　driving　force　for　accelerating　the　separation　of　photocharge　carriers　on　the　surface　of　Bi2MoO6　(ηsurf　≈71%).　They　can　also　cooperatively　reduce　the　surface　work　function　of　Bi2MoO6,　facilitating　the　migration　of　carrier　to　the　surface.　Meanwhile,　surface-integrated　Ov　and　CuxO　nanodots　allowing　dual　catalytic　sites　strengthens　the　adsorption　and　activation　CO2　into　*CO2　over　Bi2MoO6,　considerably　boosting　the　progression　of　CO2　conversion　process.　In　the　absence　of　co-catalyst　or　sacrificial　agent,　Bi2MoO6　with　Ov　and　CuxO　nanodots　achieves　a　photocatalytic　CO　generation　rate　of　12.75 µmol　g−1　h−1,　a　remarkable　increase　of　over　≈15　times　that　of　the　original　counterpart.　This　work　provides　a　new　idea　for　governing　charge　movement　behaviors　and　catalytic　reaction　thermodynamics　on　the　basis　of　synergistic　improvement　of　electric　field　and　active　sites　by　coupling　of　the　internal　defects　and　external　species.　©　2024　Wiley-VCH　GmbH.