Hydrogen　production　from　solar　water　splitting　over　semiconductors　shows　great　potential　in　solving　the　urgent　energy　and　environmental　issues,　but　its　energy　conversion　efficiency　is　always　restricted　by　the　insufficient　utilization　of　photogenerated　charge　carriers.　Introducing　built-in　electric　fields　is　a　promising　strategy　for　achieving　efficient　charge　utilization　in　photocatalysts.　However,　the　representative　examples　of　built-in　electric　fields　reported　to　date　all　have　their　own　insurmountable　shortcomings.　Herein,　we　demonstrated　that　the　zincblende-wurtzite　(ZB-WZ)　superlattice　structure　which　widely　spreads　in　II-VI　and　III-V　group　semiconductors　is　a　promising　candidate　for　the　sufficient　utilization　of　photogenerated　charge　carriers.　We　developed　the　ZB-WZ　superlattice　structures　in　a　model　semiconductor　photocatalyst,　Cd1-xZnxS,　by　employing　the　oriented-attachment　growth　mechanism,　and　realized　highly　efficient　photocatalytic　hydrogen　production　under　visible　light　irradiation　with　an　excellent　apparent　quantum　yield　of　48.7%　at　425　nm.　Then　the　huge　impact　of　the　ZB-WZ　superlattice　structure　on　the　photocatalytic　performance　was　proved　by　the　strong　reciprocal　relationships　between　the　percentage　of　the　nanocrystals　with　superlattice　structures　and　the　photoluminescence　intensity,　as　well　as　that　between　the　photoluminescence　intensity　and　the　photocatalytic　activity.　Moreover,　theoretical　simulation　demonstrated　that　the　spatial　separation　and　alternate　accumulation　of　electrons　and　holes　around　ZB/WZ　interfaces　is　dominated　by　the　polarization-induced　saw-tooth　potential　distribution　in　the　ZB-WZ　superlattice　rather　than　the　staggered　band　alignment,　and　the　intensities　of　built-in　electric　fields　in　adjacent　ZB　and　WZ　segments　can　be　tuned　by　changing　the　specific　configuration　of　the　ZB-WZ　superlattice.　These　findings　open　a　new　pathway　for　the　development　of　novel　and　efficient　semiconductor　photocatalysts　by　tuning　the　superlattice　structure　with　atomic　precision,　which　will　greatly　benefit　the　solar　water　splitting　area.