Novel luminescent ternary organic–inorganic–polymeric hybrid material has been assembled by Eu3+ complex incorporating into poly (methyl methacrylate) (PMMA) matrix. The functionalized silylated precursor PDC-Si derived from PDC (2,6-pyridinedicarboxylic acid chloride) behaves as the coordination units of Eu3+ ion. The organic polymer was introduced into the system by directly dissolving PMMA in solution of Eu(PDC-Si)3 complex and N-N-Dimethyl Formamide (DMF) with subsequent addition of tetraethoxysilane to promote hydrolysis and condensation. The structure and photophysical properties of the resulting hybrids are characterized by Fourier transform infrared spectra, X-ray diffraction (XRD), scanning electronic microscopy and photoluminescence spectra. The luminescence quantum yield was calculated based on the emission spectra and luminescence lifetimes. XRD reveals its amorphous structure. Efficient energy transfer process occurs between PMMA and Eu3+, and replacement of water molecule by PMMA in the first coordination sphere was confirmed by comparing with the binary hybrid.