Rare earths (REs) incorporated in glasses, mostly in the form of RE3+ ions, have several applications such as lasers and optical amplifiers, spectral conversion layers for solar cells, light emitters and sensors. In this context, both the composition and the structural properties of the glass, as well as the dopant concentration play an important role in determining the optical properties and the efficiency of the system. Usually, the concentration of REs is small, below 1 at%, to avoid clustering and optical quenching. In this paper, we report the case of sol-gel Eu-doped silica-soda glass films. The addition of soda to silica can reduce RE clustering and precipitation, according to molecular dynamic simulations, but brings structural instabilities to the network. Here, sodium was varied from 10 to 30 at% and Eu from 0 to 8 at%. It was shown that Eu plays a significant role in the stabilization of the matrix, improving the transparency, the refractive index and the thickness of the films. The increase of Eu concentration provides a decrease of site symmetry and an increase of quantum efficiency (QY), reaching 71% for the highest 8 at% Eu doping, with remarkable absence of concentration quenching.