Hybrid nanosilicas constitute a broad study field. They find application as catalysts, pigments, drug delivery systems, and biomaterials, among others, and it is possible to obtain them via the sol-gel methodology. Lanthanide ions present special properties like light emission. Their incorporation into a silica matrix can enhance their luminescent properties, which enables their application as luminescent markers. This work reports on (i) the preparation of luminescent spherical hybrid silica nanoparticles by the hydrolytic sol-gel methodology, (ii) doping of the resulting matrix with the europium(III) ion or its complex with 1,10-phenanthroline, and (iii) characterization of the final powders by scanning electron microscopy, infrared spectroscopy, X-ray diffraction, and europium(III) ion photoluminescence. The synthesized materials consisted of hybrid, amorphous, polydispersed nonspherical silicas with average size of 180 nm. Photoluminescence confirmed incorporation of the europium(III) ion and its complex into the silica matrix-the ligand-metal charge transfer band emerged in the excitation spectra. The emission spectra presented the bands corresponding to the transition of the excited state (5)D0 level to (7)FJ (J = 0, 1, 2, 3 and 4). The main emission occurred in the red region; the lifetime was long. These characteristics indicated that the prepared nanospherical hybrid silicas could act as luminescent markers.