Simulating　photosynthesis　to　convert　CO2　into　valuable　chemicals　is　an　effective　strategy　to　achieve　sustainable　carbon　recycles,　and　the　high　conversion　efficiency　and　selectivity　of　photocatalytic　conversion　CO2　to　specific　chemicals　are　the　key　challenges.　Herein,　a　direct　Z-scheme　Bi2WO6/La2Ti2O7　photocatalyst　is　successfully　synthesized　by　electrostatic　self-assembly　method.　The　selectivity　of　CO2　reduction　to　CO　is　improved　from　74%　of　La2Ti2O7　to　nearly　100%,　and　the　CO　yield　is　7.5　times　that　of　individual　La2Ti2O7.　The　improvement　of　the　photocatalytic　performance　is　attributed　to　the　formation　of　Z-scheme　heterojunction　between　Bi2WO6　and　La2Ti2O7,　which　facilitates　the　separation　and　transfer　of　photogenerated　carriers.　This　work　provides　a　new　insight　for　the　construction　of　efficient　photocatalyst　for　selective　reduction　of　CO2　to　CO.