A series of novel organic/inorganic rare earth (europium, terbium) hybrid materials through the coordination bond and covalent bond are synthesized and form an inorganic Si–O–Si by the sol-gel process. Mercapto-functionalized 4-mercaptobenzoic acid (MBA-Si) is obtained by using MBA and 3-(triethoxysilyl)-propyl isocyanate (TESPIC) as an organic bridge molecule, and then the carboxyl group of the precursor MBA-Si is used to modify the titanium dioxide, so as to sensitize the luminescence of rare earth ions. CdS-TiO2 is added to observe the influence of photoluminescence. 3-mercaptopropyltrimethoxysilane (MPS) is also used to modify the CdS quantum dot and obtain MPS functionalized MPS-CdS nanocomposite. These multicomponent hybrids with double cross-linking siloxane (MBA-Si) covalently bonding MPS-CdS are characterized. Subsequently, 1,10-phenanthroline (Phen) and 2,2,-bipyridyl (Bipy) as the assistant ligands together with water molecules are introduced into the rare earth hybrid system. The FT-IR, X-ray diffraction, UV–Vis, thermogravimetry and especially the photoluminescence properties of them are studied in detail.