2-Thenoyltrifluoroacetone (TTA) was grafted onto the coupling agent 3-(triethoxysilyl)-propyl isocyanate (TEPIC) through a hydrogen transfer addition reaction to construct the multifunctional bridge precursor. Other kinds of polymeric precursors (PVPD, PMAA, and PVPDMAA) were synthesized through the addition polymerization reactions using the monomer 4-vinylpyridine and methacrylic acid as the raw materials. The lanthanide compound was then assembled by the coordination effect between precursors and europium ions with the carbonyl, carboxyl groups, or nitrogen atoms. At last, we have utilized the first precursor hydrolyzed with the tetraethoxysilane (TEOS) via the sol-gel copolycondensation process to obtain three kinds of final hybrid polymers. The photoluminescence and microstructural, thermal, and mechanical properties were characterized and the results reveal that the hybrid materials imbedded into the single polymer (PVPD and PMAA) show more efficient intramolecular energy transfer between the europium ion and the modified ligand TTA-Si, bringing the excellent characteristic emission of europium ion. The different configuration of the polymeric precursor introduces a vital different appearance in the microstructure, and the hybrid material with PVPD shows the highest luminescence quantum efficiency and longest lifetime.