This publication offers an economically promising method of persistent luminescent silicate glass synthesis that does not involve high temperatures or ready-made (separately synthesized) PeL particles. In this study, we demonstrate the formation of SrAl2O4doped with Eu, Dy, and B in a SiO2glass structure using the one-pot low-temperature sol–gel synthesis method. By varying the synthesis conditions, we can use water-soluble precursors (e.g., nitrates) and a dilute aqueous solution of rare-earth (RE) nitrates as starting materials for SrAl2O4synthesis, which can be formed during the sol–gel process at relatively low sintering temperatures (600 °C). As a result, translucent, persistently luminescent glass is obtained. The glass shows the typical Eu2+luminescence and the characteristic afterglow. The afterglow duration is about 20 s. It is concluded that the slow drying procedure (2 weeks) is optimal for these samples to sufficiently get rid of the excess water (mainlyOH groups) and solvent molecules that can influence the strontium aluminate luminescence properties and have a pernicious effect on the afterglow. It can also be concluded that boron is playing a crucial role in the formation of trapping centers needed for PeL processes in the PeL silicate glass.