Novel organic-inorganic mesoporous luminescent polymeric hybrid materials containing lanthanide (Eu3+, Tb3+) complexes covalently bonded to mesoporous silica SBA-15 have been successfully prepared by co-condensation of the modified 2-thenoyltrifluoroacetone (TTA-Si) and tetraethoxysilane (TEOS) in the presence of Pluronic P123 surfactant as a template. 2Z-Thenoyltrifluoroacetone (TTA) was grafted onto the coupling agent 3-(triethoxysilyl)-propyl isocyanate (TEPIC) and used as the first precursor, and the other precursor PMMA was synthesized through the addition polymerization reaction of the monomer methyl methacrylate. Then these precursors coordinated to rare earth ions, and the final mesoporous polymeric hybrid materials Ln(TTA-SBA-15)(3)PMMA (Ln = Eu, Tb) were obtained after hydrolysis and copolycondensation with the tetraethoxysilane (TEOS) via a sol-gel process. In addition, for comparison, SBA-15 covalently bonded with the binary Ln(3+) complexes with TTA ligand were also synthesized, denoted as Ln(TTA-SBA-15)(3) (Ln = Eu, Tb). All of these hybrid materials have high surface area, uniformity in the mesostructure, and good crystallinity. The detailed luminescence studies on all the materials showed that the ternary rare-earth mesoporous polymeric hybrid materials present stronger luminescent intensities, longer lifetimes, and higher luminescent quantum efficiencies than the binary rare-earth mesoporous hybrid materials, indicating that the introduction of the organic polymer chain is a benefit for the luminescence properties of the overall hybrid system.