The mesostructured lamellar phases with the general formula [C (n) H2n+1N(CH3)(3)](3)[Fe(CN)(6)] (n = 14, 16, 18) were prepared by ion-exchange/precipitation reaction of alkyltrimethylammonium surfactants and K-3[Fe(CN)(6)] complex in aqueous medium. The phases were characterized using powder X-ray diffraction, high-resolution transmission electron microscopy, IR spectroscopy, thermogravimetric, and differential scanning calorimetry means. The results obtained all support a proposed model of crystal structure for these materials, in which the layers are constructed by monolayer of the discrete complex molecules, and the surfactants tails of opposite head groups deeply penetrate and arrange with a tilt angle of 63A degrees.