Mesostructured composites of layered perovskites and cationic surfactants were synthesized . Layered perovskite HCa2N13, 3010 and alkyltrimethylammonium (CnTMA) or alkylpridinium (CnPy) surfactants formed lamellar-type composites. The interlayer spacings of the composites increased with increasing carbon number of alkyl group in the surfactants. The spacings were also affected by the Nb: surfactant ratio in the reacting solutions. From comparison between size of molecule and interlayer spacing, it is suggested that two types of composites formed, which contain C16Py + ions with mono-or bilayer arrangements .