Current　heterojunction　photocatalysts　suffer　from　sluggish　charge　transfer　due　to　the　discontinuous　interfaces　at　an　atomic　level.　Herein,　we　report　a　NiO–Co3O4　ultrathin　lateral　heterojunction　using　NiCo-based　bimetal–organic　layers　as　precursors.　The　atomic-resolution　images　display　a　unique　continuous　semi-coherent　interface　between　NiO　and　Co3O4.　The　experimental　results　confirm　that　the　continuous　semi-coherent　interfaces　effectively　expedite　the　electron　transfer　from　NiO　to　Co3O4.　Concomitantly,　the　electron　transfer　raises　d-band　center　of　Co3O4　in　NiO–Co3O4　toward　Fermi　level,　as　revealed　by　the　density　functional　theory　calculations.　As　a　result,　the　*COOH　intermediate　can　be　strongly　bound　on　cobalt　reactive　centers.　The　successful　modulation　of　charge　transfer　and　intermediate　binding　by　continuous　semi-coherent　interfaces　leads　to　a　remarkable　gas　yield　of　22.67　mmol　h−1　from　photocatalytic　CO2　reduction　over　NiO–Co3O4.　This　work　highlights　the　crucial　roles　of　interface　engineering　in　regulating　carrier　kinetics　and　surface　reactions.　©　2023　Elsevier　B.V.