Novel transparent glasses and glass-ceramics were fabricated by using melt-quenching technique with the following composition: TeO2–WO3–Nb2O5–KF–La2O3 doped with Tm2O3. Different properties and physical parameters of these glasses were investigated. As the concentration of Tm3+ ions increases, the linear refractive index increases while the optical energy gap decreases. With high Tm3+ ion concentration creates nucleation in the glass matrix this was investigated by x-ray diffraction. The Judd-Ofelt parameters used to calculate the electric and magnetic dipole transition probabilities, branching ratios, and radiative lifetimes of various excited states of Tm3+-doped parent glass. The emission cross section values for the 3F4→3H6 transition computed by using the McCumber hypothesis. The stimulated emission cross section σeFL(λ) and gain values of fabricated glass increase with Tm3+ ions. The spectroscopic quality and figure of merit (FOM) gain (σeFL(λ)×τR) factors were evaluated for the prepared transparent glass. Furthermore, the produced glasses were demonstrated to have low OH content and they have high fluoride ion content. These important properties of the glasses and glass-ceramics make them suitable for use in photonic applications.