Abstract: Intercalation behavior of n-alkylamines into a protonated form of an A-site defective layered perovskite H2W2O7 has been investigated. Results from XRD indicate these materials are layered with the corresponding interlayer spacing governed by the n-alkylamine chain length, and a reversible intercalation and deintercalation property is observed among these intercalation compounds. The IR spectra of the intercalation compounds with n-alkylamines clearly show that n-alkyl chains possess an all-trans conformation, and H2W2O7 accommodate n-alkylamines (C n H2 n +1NH2: n=3, 4, 7, 8, 12, 16) to form intercalation compounds via an acid–base mechanism. A linear relationship between the interlayer distance and the number of carbon atoms in n-alkyl chains is observed to show a bilayer arrangement of the n-alkyl chains with a tilt angle of ∼71.6°. Elemental analysis studies reveal that the amounts of intercalated n-alkylamines are about 2.0mol per [W2O7]. Despite the surface geometry of H2W2O7 is almost identical to those of layered perovskites H2[An −1 Bn O3 n +1], the amounts of intercalated n-alkylamines of them are different. A reasonable explanation is given through our research. [Copyright &y& Elsevier]