This study explores the solution-state behavior of Hydrogen-Bonded Organic Frameworks (HOFs) and their application in fabricating continuous, high-crystalline membranes. HOFs, a type of porous material, are found to fragment into small particles while maintaining their original assemblies when dispersed in solvents, as confirmed by Cryo-electron microscopy and 3D electron diffraction. The unique solution processibility allows for the fabrication of diverse continuous HOF membranes with high crystallinity and porosity through a solution-casting approach on various substrates. Among these, the HOF-BTB@AAO membrane exhibits high C3H6 permeance (1.979 × 10−7 mol·s−1·m−2·Pa−1) and excellent separation performance for C3H6 and C3H8 (SF = 14). This membrane presents a green, low-cost, and efficient separation technology with potential applications in petroleum cracking and purification. The study also highlights the importance of understanding the aggregation state of HOFs in solution for optimizing membrane growth and fabrication technology.This study explores the solution-state behavior of Hydrogen-Bonded Organic Frameworks (HOFs) and their application in fabricating continuous, high-crystalline membranes. HOFs, a type of porous material, are found to fragment into small particles while maintaining their original assemblies when dispersed in solvents, as confirmed by Cryo-electron microscopy and 3D electron diffraction. The unique solution processibility allows for the fabrication of diverse continuous HOF membranes with high crystallinity and porosity through a solution-casting approach on various substrates. Among these, the HOF-BTB@AAO membrane exhibits high C3H6 permeance (1.979 × 10−7 mol·s−1·m−2·Pa−1) and excellent separation performance for C3H6 and C3H8 (SF = 14). This membrane presents a green, low-cost, and efficient separation technology with potential applications in petroleum cracking and purification. The study also highlights the importance of understanding the aggregation state of HOFs in solution for optimizing membrane growth and fabrication technology.