Covalent organic framework (COF) membranes hold potential for widespread applicability,b ut scalable fabrication is challenging.H ere,w ed emonstrate the disorderto-order transformation from amorphous polymeric membrane to crystalline COF membrane via monomer exchange. Solution processing is used to prepare amorphous membrane and the replacing monomer is selected based on the chemical and thermodynamical stability of the final framework. Reversible imine bonds allowt he extraneous monomers to replace the pristine monomers within amorphous membrane,d riving the transformation from disordered network to ordered framework. Incorporation of intramolecular hydrogen bonds enables the crystalline COF to imprint the amorphous membrane morphology.T he COF membranes harvest proton conductivity up to 0.53 Scm À1 at 80 8 8C. Our strategy bridges amorphous polymeric and crystalline COF membranes for large-scale fabrication of COF membranes and affords guidance on materials processing.
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