A series of ternary rare earth complexes were covalent grafted to the inorganic Si–O networks through the novel bifunctional silylated monomer BBMSSi (BBMS = Bis [benzoylmethyl] sulfoxide). FT–IR, NMR, XRD, TGA, SEM, DRS and photoluminescence properties were used to characterize the obtained hybrid materials. Scanning electron micrograph results revealed hybrids exhibiting homogeneous morphology with large particle size of 100–200 μm and no phase separation. Photoluminescence measurements indicated hybrids with characteristic red and green luminescence. In addition, the existence of the polymeric chain PMMA and 1,10-phenanthroline in different hybrid systems present different microstructure and luminescence behavior.