In the present work, a series of Sm3+ doped transparent strontium aluminate glasses with the composition Al2O3-(3-x)SrO: xSm3+ (x = 0, 0.01, 0.03, 0.06, 0.1, 0.2) were fabricated by a containerless process using an aerodynamic levitation furnace. The structural characteristics, density, Vicker’s hardness, and thermal and spectroscopic behaviors of these glasses were investigated. All the glasses exhibit excellent thermal stabilities (Tg ≥ 792 °C) and the glass-forming ability is enhanced with the increasing content of Sm3+. The emission spectra recorded under an excitation of 404 nm show four emission transitions as a result of 4G5/2 translated to the lower states of 6H5/2, 6H7/2, 6H9/2, and 6H11/2, and a bright orange-reddish luminescence can be observed in Al2O3-(3-x)SrO: xSm3+ glasses. The high thermal stability, good glass-forming ability and excellent hardness provide new options for the development of visible orange-reddish lasers and smart photoluminescent glass coating materials.