Covalent organic frameworks (COFs) with well-ordered pore structures and versatile functionalities hold tremendous promise as membrane building blocks. The facile and controllable fabrication of COF membranes remains a critical challenge. Herein, we presented a one-step vapor-liquid interfacial polymerization (VLIP) method to in-situ fabricate COF membranes on substrates under mild conditions. This VLIP method features controllable COF growth at the vapor-liquid interface, acquiring COF membranes with tunable physicochemical structure. The time-dependent amorphous-to-crystalline COF growth improved the crystallinity of COF membranes, thus improving the molecular sieving property. The increased monomer concentration endowed COF membranes with higher hydrophilicity, intensifying the water sorption ability. The resultant COF membranes conferred numerous hydrophilic pathways for water-selective transport, exhibited a high and stable n-butanol dehydration performance with permeation flux of 8160 g m⁻² h⁻¹ and separation factor of 1023 over 14 days. This VLIP method may evolve into a generic platform technique to fabricate COF membranes for efficient molecular separation.

具有有序孔结构和多功能功能的共价有机框架 (COF) 作为膜构建块具有巨大的前景。COF 膜的简便和可控的制造仍然是一个关键的挑战。在此，我们提出了一种一步汽液界面聚合（VLIP）方法来原位在温和条件下在基板上制造 COF 膜。这种 VLIP 方法在汽液界面具有可控的 COF 生长，获得具有可调理化结构的 COF 膜。随时间变化的无定形到结晶 COF 生长提高了 COF 膜的结晶度，从而提高了分子筛分性能。增加的单体浓度赋予了 COF 膜更高的亲水性，增强了吸水能力。所得的 COF 膜为水选择性传输提供了许多亲水途径，表现出高且稳定的正丁醇脱水性能，渗透通量为 8160 g m ^-2  h ^-114 天的分离系数为 1023。这种 VLIP 方法可能会演变成一种通用的平台技术，以制造用于有效分子分离的 COF 膜。