Good optical quality Eu3+-doped silica-polyethyleneglycol hybrids were prepared by the sol-gel process. Thermomechanical analysis showed an increase of the glass transition temperature, due to the stiffness of the polymeric network, as the amount of Eu3+ increased. Europium luminescent properties were used to study structural evolution during the sol-gel transition. For lower doping concentrations dried gels present statistical distributions of Eu3+, typical of an amorphous environment, while for higher concentrations a crystalline-like environment of Eu3+ was observed. A broad emission band was observed in the visible part of the electromagnetic spectrum and assigned to the intrinsic emission from the hybrid polymeric network.