Titanosilicate was modified by interlayer surface silylation using octyltriethoxysilane (OTES) and dodecylamine (DDA) in ethanol without a pre-swelling step. The introduction of silyl groups into the interlayer region was confirmed by XRD, FT-IR, RAMAN, SEM, TGA, 29 Si NMR and TEM. DDA acts as a gallery expander and silylation catalyst. The evaporation of ethanol from the dispersion yields well-ordered silylation. Layered titanosilicate silicate with large basal spacings between 2.95 and 3.87nm were investigated. The layered structures of the silylated products were confirmed by swelling behavior upon attachment of alkylsilyl groups. Solid-state 29 Si MAS NMR of the silylated samples showed Q 3 and Q 4 signals as well as T 2 signals. The increase in the relative intensity of Q 4 for Q 3 and the appearance of a T 2 signal was attributed to the grafting of OTES to the interlayer surface silanol groups. This method provides a promising route for the preparation of new functional nanomaterials to bond a variety of functional groups to the interlayer surface of layered materials.