Lanthanum barium borate glasses doped with praseodymium were fabricated by a melt-quenching process, to study the effect of Pr2O3 on their properties. The addition of Pr₂O₃ in glass increases its density, molar volume, and refractive index. XRD confirms an amorphous nature of glass network, and XANES approves the praseodymium character as Pr3+ oxidation state in glass. Glasses absorb photons in ultraviolet and near-infrared region by the Pr3+ transitions from 3H4 ground state. The photoluminescence spectra of glasses exhibit the strongest emission at 602 nm (1D2 → 3H4) under 442 nm excitation (3H4 → 3P2). The optimal 0.5 mol% Pr2O3-doped glass possesses the highest emission intensity due to the concentration quenching effect. Judd-Ofelt theory was used to determine the Pr3+ site environment in glass and its dominant stimulated emission. Strong orange emission of this glass is suitable for orange solid-state lasers, LEDs, and emitting devices.