According to coordination chemistry principle and molecular assembly technology, series of ternary lanthanide centered hybrid systems have been constructed through coordination bonds. Among one component (ligand) is organically modified Si–O network, which originates from the functional molecular bridge (BFPPSi) by the functionalization of 1,3-bis(2-formylphenoxy)-2-propanol (BFPP) with 3-(triethoxysilyl)propyl isocyanate. In the second component (ligand), three different organic polymeric chains are introduced, poly-(methyl methacrylate) (PMMA, from the polymerization of MMA with the benzoyl peroxide [BPO] as the initiator), poly-(methyl acrylic acid) (PMAA, from the polymerization of MAA with the BPO as the initiator), polyvinyl pyridine, respectively. All these ternary hybrid materials show homogeneous, regular microstructure, suggesting the existence of assembly process of lanthanide centers, inorganic Si–O network and organic polymer chain. Compared to the binary hybrids without polymer chain, the photoluminescent properties of these ternary hybrids present stronger luminescent intensities, longer lifetimes and higher luminescent quantum efficiencies indicating that the introduction of organic polymer chain is favorable for the luminescence of the whole hybrid systems.