Glasses may be prepared by sol-gel processing over a wide range of compositions and thick multilayer deposits may be used as waveguides for integrated optics. Doping these layers with rare-earth (RE) ions enables the fabrication of active devices for optical amplifiers; the incorporation of these ions into nanocrystallites offers possibilities for increased dopant concentration without fluorescence quenching, improved spectroscopic performance and high quantum yields. Rare-earth (RE) ions such as erbium (Er 3+ ), ytterbium (Yb 3+ ), neodymium (Nd 3+ ), thulium (Tm 3+ ), holmium (Ho 3+ ) and praseodymium (Pr 3+ ) have been widely used in optical applications and cover a range of wavelengths ranging from UV-visible to the near infrared. This chapter includes basic principles of fluorescence in RE doped glasses, fluorescence lifetimes, quantum yields and Judd-Ofelt analysis. A few information is given about the preparation and characterization of glasses, thin films and glass-ceramics (nanocrystallites embedded in glass matrix) prepared by sol-gel processing. The growth of nanocrystals in glassy sol-gel films through suitable heat treatments can avoid the influence of high phonon energy of silica glasses. The characterization of such materials can be evaluated by optical techniques, namely UV-Visible, FTIR, among other additional techniques that include Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD) and Atomic Force Microscopy (AFM).The need for high-speed data associated with the advance of telecommunication systems by optical transmission and fiber-optic connections has contributed to extend the optical regime