Developing　high-efficiency　photocatalysts　for　CO2　photoreduction　is　one　of　the　potential　solutions　to　address　both　energy　and　pollution　issues.　In　this　study,　α-Fe2O3　modified　La2Ti2O7　was　successfully　synthesized　with　intimate　contact　between　La2Ti2O7　and　α-Fe2O3,　greatly　facilitating　the　carrier　separation　and　transfer　during　the　photocatalytic　reaction.　The　activity　and　stability　for　photocatalytic　CO2　reduction　over　α-Fe2O3/La2Ti2O7　were　significantly　improved　as　compared　with　the　La2Ti2O7　substrate.　The　optimized　3%　α-Fe2O3/　La2Ti2O7　composite　showed　excellent　CO2　reduction　activity　after　5　h　consecutive　illumination,　and　the　total　utilized　photoelectron　number　(UPN)　reached　7.76　μmol,　which　was　about　4.4　times　higher　than　that　of　the　pristine　La2Ti2O7.　The　steady-state　photoluminescence　spectra,　time-resolved　photoluminescence　spectra　(TRPL)　and　photocurrent　response　results　showed　that　the　improved　charge　separation　efficiency　was　the　key　factor　to　enhance　the　photocatalytic　activity.　This　work　provides　novel　insights　into　the　design　and　fabrication　of　photocatalysts　of　high　performance　for　CO2　reduction　for　solar-to-energy　applications.　©　The　Royal　Society　of　Chemistry.