In this paper, the functionalized monomer (TFAASi) behaves as a linkage to be immobilized into inorganic composite host gels through covalent bonds. Subsequently two kinds of Eu-centered chemically bonded hybrid gels (Eu-TFAA-Si-O-Ti, Eu-TFAA-Si-O-B) with composite hosts have been prepared and characterized. The covalently bonded Si-O-B hybrid gel presents stronger red/orange intensity ratio, longer lifetimes and higher quantum efficiency than covalently bonded Si-O-Ti one, suggesting that SiO2-B2O3 composite gel is more suitable for the emissions of Eu3+ than SiO2-TiO2 composite gels.