The one-step room-temperature micropatterning of a fluorophore-doped xerogel material on silicon oxide substrates is reported. The organo-alkoxysilane precursors and organic fluorescent dyes, as well as the polymerization experimental conditions, were tailored in order to obtain a highly homogeneous transparent material suitable for photonic applications. A thorough structural characterization was carried out by Fourier transform infrared (FT-IR) spectroscopy, (29)Si nuclear magnetic resonance ((29)Si NMR), thermogravimetric analysis (TGA), N(2) adsorption Brunauer-Emmett-Teller (BET) porosimetry, and confocal microscopy. These studies revealed a stable nonporous highly cross-linked polymer network containing evenly dispersed fluorescent molecules. Xerogel microstructures having thicknesses between 4 and 80 μm and height-to-width ratios between 0.04 and 4, as well as showing different geometries, from well arrays to waveguides, were patterned in a single step by micromolding in capillaries (MIMIC) soft lithographic technique. The reliability of the replication process was tested by bright-field optical microscopy and scanning electron microscopy (SEM) that show the close fidelity of the microstructures to the applied mold. The optical performance of the developed material was demonstrated by fabricating waveguides and evaluating their corresponding spectral response, obtaining absorption bands, at the expected excitation wavelengths of the corresponding fluorescent dyes and gain due to photonic re-emission (fluorescence) at their corresponding dye emission wavelengths. The hybrid xerogel material and the application of the simple fabrication technology presented herein can be directly applied to the development of cost-effective photonic components, as could be light emitters, to be readily integrated in single-use lab-on-chip devices and other polymeric microsystems.