摘要: Efficient spatial separation and orderly migration of charge carriers, as well as robust kinetics at catalytic sites, constitute the fundamental and core issues in enhancing the conversion of solar energy into hydrogen from water splitting. Herein, surface localization polarization engineering has been confirmed to be effective to accelerate the oriented charge migration dynamics behaviour and collaboratively activate redox crystal facets on the constructed Co3O4/In2S3 S-scheme heterojunction. Theoretical calculations and ultrafast atomic-scale spatiotemporal analysis demonstrate that, Co3O4/In2S3 heterojunction endows the surface localized field pointing from the hexagonal In2S3{102} to cubic Co3O4{111} with an increased field strength on the basis of Co3O4 from 0.27 μV to 2.19 μV and lifetime from 260.99 ns to 975.18 ns for charge carrier transfer to the surface of the redox crystal facets. Polarization-state charge uneven distribution reduces and enhances the binding energy of components on active crystal facets thus with correspondingly increasing and decreasing onsite electron density for promoting chemical adsorption of *H and *OH, respectively. Solar to H2 of 1.32% at AM 1.5G is achieved along with high photocatalytic stability. Surface polarization engineering plays a pivotal role in our study, enabling substantial tuning of charge transfer behavior and crystal facet surface activation within S-scheme heterojunctions for the improved photocatalytic H2 generation.