Abstract New types of intercalated complexes are synthesized by the reaction of MPS3 layer crystals (M=Mg, Zn, Mn) with n-alkylamines (CnH2n+1NH2, n=1–8). The amines are adsorbed on the interlamellar surfaces of the MPS3 crystals to form two different types of complexes of increased values in basal spacing. The spacing value of the first type of complexes is independent of the number of carbon atoms in alkyl chain of the amines, and the value of the second type of complexes increases with the number of the carbon atoms. The possible arrangements of the amines in the interlayer region are proposed for these types of complexes.