Lamellar organoammonium silicates with variable silicon environments have been synthesized by the reaction of a layered polysilicate kanemite with aqueous solutions of hexadecyltrimethylammonium (C(16)TMA) chloride. While the structure of kanemite is composed of only Q(3) silicate species ((SiO)(3)SiO), SiO4 units with both Q(3) and Q(4) ((SiO)(4)Si) environments were present in the silicate frameworks of the lamellar C(16)TMA silicates. The Q(4) species mainly formed by intralayer condensation of the Q(3) species in the individual silicate sheets in kanemite rather than by interlayer condensation between the adjacent sheets. The intralayer condensation can be suppressed by lowering the reaction temperature and/or shortening the reaction time, which results in the relative retention of the silicate framework of kanemite in the lamellar C(16)TMA silicates.