Keggin-type polyoxotungstate hybrid layered crystals are successfully synthesized in a single phase by using a heterocyclic surfactant. Heteropolyoxotungstate anions of [XW 12 O 40 ] n-(XW 12 , X = P, Si; n = 3, 4) are hybridized with the dodecylpyridazinium (C 12 pda) cation. Single-crystal X-ray diffraction analyses reveal that all of the countercations of XW 12 are replaced by C 12 pda cations. The layered structures consist of XW 12 inorganic layers and C 12 pda organic layers, stacked al- [a]