A novel azobenzene derivative modified magadiite has been prepared by the reaction between the interlayer hydroxyl groups of magadiite and the azobenzene derivative using dodecyltrimethylammonium-exchanged magadiite as the intermediate. The formation of the silylated magadiite-azobenzene system was confirmed by X-ray diffraction, IR and MAS NMR spectroscopies. The organic groups of the azobenzene molecules are grafted onto the interlayer surface of magadiite by covalent bonding, affording compounds different from those derived by ion exchange. The orientation and reorientation of the azobenzene derivative in the magadiite have been examined through observing its photoinduced anisotropy behavior.