HighlightsIt is the first attempt to combine covalent organic frameworks with hexagonal boron nitride (h-BN) to construct efficient metal-free photocatalyst.The composite displays superior photocatalytic hydrogen production performance in metal-free systems.The integrated poroush-BN can suppress electron backflow to optimize the composite photocatalytic activity.Supplementary InformationThe online version contains supplementary material available at 10.1007/s40820-023-01100-x.