Zinc sulfide (ZnS) quantum dot is modified with 3-mercaptopropyltrimethoxysilane (MPTMS) to obtain MPTMS functionalized SiO2/ZnS nanocomposite. Novel rare earth/inorganic/organic hybrid materials are prepared by using 3-(triethoxysilyl)-propyl isocyanate (TESPIC) as an organic bridge molecule that can both coordinate to rare earth ions (Eu3+, Tb3+, Sm3+ and Dy3+) and form an inorganic Si–O–Si network with SiO2/ZnS nanocomposite after cohydrolysis and copolycondensation through a sol-gel process. These multicomponent hybrids with double cross-linking siloxane (TESPIC-MPTMS) covalently bonding SiO2/ZnS and assistant ligands (Phen = 1,10-phenanthroline, Bipy = 2,2′-bipyridyl) are characterized and especially the photoluminescence properties of them are studied in detail. The luminescent spectra of the hybrids show the dominant excitation of TESPIC-MPTMS-SiO2/ZnS unit and the unique emission of rare earth ions, suggesting that TESPIC-MPTMS-SiO2/ZnS unit behaves as the main energy donor and effective energy transfer take place between it and rare earth ions. Besides, the luminescent performance of Bipy-RE-TESPIC-MPTM-SiO2/ZnS hybrids are superior to that of Phen-RE-TESPIC-MPTMS-SiO2/ZnS ones (RE=Eu, Tb, Sm, Dy), which reveals that Bipy or Phen only act as structural ligand within the hybrid systems.