Abstract Rare earth (Eu/Sm) doped silica–titania composite systems were sensitized by sol–gel method in solid and powder forms. The crystalline phase has been identified for the annealed samples at 1000°C by X-ray diffraction (XRD). The bonding formation of the host matrix was examined by Fourier transform infrared (FTIR). The fingerprint transition lines of Eu3+ ions, with the main emission line at 616nm, are recorded for the samples. Improvement in Eu3+ luminescence has been recorded by adding Sm3+ and by samples. Violet emission is observed under UV irradiation. Violet–blue upconversion luminescence is recorded at room temperature.