SrAl2O4:Eu(2+), Dy(3+) has been extensively studied for industrial applications in the luminescent materials field, because of its excellent persistent luminescence properties and chemical stability. Traditionally, this strontium aluminate material is synthesized in bulk form and/or fine powder by the classic solid-state method. Here, we report an original synthetic route, a molten salt assisted process, to obtain highly crystalline SrAl2O4 powder with nanometer-scale crystals. The main advantages of salt addition are the increase of the reaction rate and the significant reduction of the synthesis temperature because of much higher mobility of reactants in the liquid medium than in the solid-state method. In particular, the formation mechanism of SrAl2O4, the role of the salt, and the phase's evolution have been explored as a function of temperature and time. Phosphorescent powders based on SrAl2O4:Eu(2+), Dy(3+) with high crystallinity are obtained after 1 h treatment at 900 °C. This work could promote further interest in adopting the molten salt strategy to process high-crystallinity materials with enhanced luminescence to design technologically relevant phosphors.