Sol–gel materials based on SiO2 and TiO2 precursors are attractive as a new platform for planar photonics. Particularly interesting are those based on organically modified silica (ORMOSIL), which may improve the luminescent properties of organic dyes. However, their microstructurization remains a challenge as it requires optimization of various technological stages. Here, we report the structurization of thin layers based on ORMOSIL precursor and titanium(IV) ethoxide (TET) containing luminescent rhodamine B (RhB) dye. Films were fabricated using sol–gel synthesis and dip-coating method. Depending on the time of annealing performed at 200 °C, layers with different thicknesses (300–760 nm) and refractive indices (RI) (1.51–1.68) were obtained. Combining photolithography and wet-chemical etching processes made it possible to fabricate well-separated sol–gel waveguides and discs of different diameters. The etching time in buffered hydrofluoric acid (BHF) affected the depth of the etched luminescent microstructures. Additionally, it was found that a longer layer’s annealing time increased the etching selectivity of the substrate over the sol–gel layer. This enabled the obtaining of under-etched sol–gel goblet microstructures. Selected samples were investigated using scanning electron microscopy (SEM). UV–Vis photoluminescence measurements showed that long heat treatment also influenced the emission spectrum’s shape. The stability of the films under ambient conditions was established using spectroscopic ellipsometry. It was proven that films heat-treated at 200 °C did not change their properties during storage time of around 2 months. Relatively high RI, luminescent properties, and structurization potential make these microstructures interesting for application in integrated photonic devices, e.g., light amplifiers or sensing systems.