The sol-gel technology allows for the development of materials for nonlinear optics and photonics through the synthesis of multifunctional ceramic materials. Although the nature of the amorphous matrix allows the material to be doped with a large amount of the active components without quenching, it may affect the spectroscopic characteristics of the dye (e.g., result in a shift of absorption and emission peaks with drying time, presumably with a change of concentration). This study presents the material (SiO2 impregnated with organic dyes—Rhodamine 6G and 19) with tunable emissions obtained by the authors upon annealing at different temperatures within the range of 100–300 °C. Possible observed effects were discussed based on spectroscopic properties and thermal studies of the synthesized material. Concerning annealing at different temperatures, an effect on concentration was observed. At the same time, a longer heating process at 300 °C revealed a protective function of sol-gel-derived silica for the organic dye; the longer heating did not cause any further significant changes in the dye’s emission, which indicates the preservative role of the sol-gel layers. Furthermore, etching tests of thin layers were conducted, resulting in smooth side edges of the waveguide. The tests have shown that it is possible to use dye-doped sol-gel layers as active components in photonics platforms.