The silylation of ilerite with p-aminophenyltrimethoxysilane (denoted as APhS) was conducted in order to attempt preparation of a layered organic-inorganic hybrid nanocomposite having interlayer microporosity, in which the APhS molecule bridges between the silicate layers using two heterofunctional groups containing an amino group and a methoxy one. The APhS molecules were successfully condensed and immobilized in the interlayer of the protonated ilerite. Chemical analysis and (29)Si solid-state NMR results indicated that the interlayer space was occupied by preferential condensation between the APhS molecules. Subsequent HCl treatment could remove the excess amounts of the oligomeric species of the APhS molecules. The removal brought about vacant spaces in the interlayer supported by the bridging of the residual APhS molecules. Furthermore, the immobilized APhS molecules had a significant influence on the surface properties of the resultant nanocomposite, which showed high toluene adsorptivity. Consequently, we found a means to construct a microporous, layered nanocomposite by the bridging of the organic spaces with two heterofunctional groups.