Lamellar mesostructured calcium phosphates constructed by ionic bonds were prepared by using n-alkylamines (n-C (n) H2n+1NH2, n = 8-18) at room temperature in the mixed solvent systems of aliphatic alcohol (C (n) H2n+1OH, n = 1-4) and water, and the synthetic conditions were investigated in detail. The mixed solvent systems suppressed the formation of crystalline calcium phosphates like brushite (CaHPO4 center dot 2H(2)O) and monetite (CaHPO4) at low temperatures, successfully affording pure lamellar mesostructured calcium phosphates. Other crystalline phases such as hydroxyapatite (Ca-10(PO4)(6)(OH)(2)) were not formed under the conditions with the Ca/P molar ratios in the range of 0.7-1.0 in the starting mixtures. The Ca/P molar ratio of the lamellar mesostructured calcium phosphates was ca. 1.0, calculated by ICP and P-31 MAS NMR data. Interestingly, the kind of alcohols strongly influenced the solubilities of calcium phosphate species and n-alkylamines, and then lamellar mesostructured phases were obtained with some morphological variation.