 Highlights it is the first attempt to combine covalent organic frameworks with hexagonal boron nitride, HBN, to construct efficient metal-free photocatalyst. The composite displays superior photocatalytic hydrogen production performance in metal-free systems. The integrated porous HBN can suppress electron backflow to optimize the composite photocatalytic activity. This article was authored by Gu Yan, Xiaodong Sun, Yu Zhong, and others.