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We orderly assembled zero-dimensional 2-methylimidazole (mim) molecules into unprecedented supramolecule array membranes (SAMs) through solvent-free vapor processing, realizing the intermolecular spacing of mim at ca. 0.30 nm available as size-sieving channels for distinguishing the tiny difference between H2 (kinetic diameter 0.289 nm) and CO2 (kinetic diameter 0.33 nm). The highly oriented and dense membranes yield a separation factor above 3600 for equimolar H2 /CO2 mixtures, which is one order of magnitude higher than those of the st