We report on the sol-gel fabrication and characterization of (100− x )SiO 2 – x SnO 2 ( x =8, 16, and 25 mol %) glass-ceramic waveguides doped with 1 mol % Eu 3+ . A suitable top-down thermal process led to the formation of SnO 2 nanocrystals ~4 nm embedding Eu 3+ ions. The excitation spectra evidence the role of interband electronic transition of SnO 2 nanocrystals on the luminescence of Eu 3+ . Monitoring the 5 D 0 → 7 F 2 Eu 3+ emission, we observe about 15 times increase in the intensity of SnO 2 absorption band, moving from x =8 to 25 mol %. These waveguides also exhibit low losses, making them quite promising for development of high-gain integrated optical amplifiers.