A layered titanoniobate, in which the interlayer of the metal oxide based on octahedral framework is pillared with silica, has been prepared from HTiNbO5 by employing alkylamines (CnH2n+1NH2, n = 4, 6, 8, 10) and tetraethylorthosilicate as interlayer exchange guests and a pillar precursor, respectively. The incorporated amine had bilayer arrangements in the interlayer space acid their ammonium head groups pointed to the host (TiNbO5-) layers. While the basal spacing of the compounds increased with the chain length of alkylamine, the inclination angle also increased. The intercalated structure facilitated the incorporation of tetraethyl-orthosilicate ate into the interlayers, and silica-pillared layered titanoniobate was obtained after calcination. The physicochemical properties of the resultant pillared compounds were characterized on the interlayer microstructure, nitrogen adsorption and UV-VIS absorption spectra.