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We introduce a “solution‐processing‐transformation” strategy, deploying solvent vapor as scaffolds, to fabricate high‐quality hydrogen‐bonded organic framework (HOF) membranes. This strategy can overcome the mismatch in processing conditions and crystal growth thermodynamics faced during the facile solution processing of the membrane. The procedure includes the vapor‐trigged in situ transformation of dense amorphous supramolecules to crystalline HOF‐16, with HOF‐11 as the transient state. The mechanism involves a vapor‐activated dissolution‐precipitation equilibrium shifting and hydrogen bonding‐guided molecule rearrangement, elucidated through combined experimental and theoretical analysis. Upon removal of the molecular scaffolds, the resulting HOF‐16 membranes showcase significant improvement in hydrogen separation performance over their amorphous counterparts and previously reported HOF membranes. The method's broad applicability is evidenced by successfully extending it to other substrates and HOF structures. This study provides a fundamental understanding of guest‐induced ordered supramolecular assembly and paves the way for the advanced manufacture of high‐performance HOF membranes for gas separation processes. [ABSTRACT FROM AUTHOR]