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Keggin-type polyoxometalates are effective catalytic materials for acid-catalyzed reactions and oxidation reactions. In this paper, we describe the fabrication of a porous membrane of Keggin-type polyoxometalates at the gas-liquid interface and the structural characterization of the membrane via aberration-corrected scanning transmission electron microscopy. The membrane is formed by the introduction of n-octylamine vapor into aqueous solution of Keggin-type silicotungstic acid (H4SiW12O4 and cesium chloride. The membrane obtained ha