Four different hybrid organic-inorganic materials based on TiO2-SiO2 matrices with organic additives and doped with rare-earth metal ions (III) from the group of europium, cerium, terbium, neodymium, dysprosium and samarium, were synthesized by sol-gel method. Tetraethyl orthosilicate, titanium (IV) isopropoxide and organic compounds, such as butyl acrylate, butyl methacrylate, ethyl acetoacetate, ethylene glycol dimethacrylate, ethyl acetate, propylene carbonate, organic solvents and certain inorganic salts were used in the synthesis. The inorganic part of the sols, which were used in the synthesis of all the hybrid materials, was prepared separately and then the organic parts were added. The materials obtained were aged for three weeks at room temperature and then heated in an electric oven for three hours at temperatures of 80 °C - 150 °C. Scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM/EDX); X-ray diffraction (XRD); Fourier transform infrared spectroscopy (KBr technique); 29Si magic-angle spinning nuclear magnetic resonance; and fluorescence spectroscopy were used for the examination of morphology, microstructure and luminescence properties, respectively. Photoluminescence properties with relatively intense narrow emission lines of Tb, Eu, Dy, Nd, Sm respectively to the RE-ions doping, were observed for all the hybrid materials.