A novel crystalline organic–inorganic hybrid aluminosilicate material was successfully synthesized using methyltrimethoxysilane as a silicon source. Ab initio crystal structure analysis using powder X-ray diffraction data elucidated that this material was composed of the ordered stacking of layered aluminosilicates similar to sodalite-type zeolites and that methyl groups bonded to silicon atoms were arrayed on the inner surface of the interlayer. This material selectively inhaled amphiphilic molecules such as alcohols to open its interlayer distance. It could even breathe ethanol vapor at quite a low pressure and extract ethanol from the aqueous solution.