This study deals with SrAl₂O₄: Eu²⁺, Dy³⁺ phosphor pigments prepared by an optimized perchlorate-assisted combustion synthesis and tested for developing glow-in-the-dark safety markings. Recipes with different oxidizer/fuel ratios were designed to create an in-situ reducing-reaction atmosphere and promote Eu³⁺ → Eu²⁺ reduction, which is responsible for the specific long-lasting, green emission of the pigments. The obtained data proved the efficiency of glycine-rich mixtures (up to 200% glycine excess), which led to improved optical features, as compared to the reference stoichiometric sample. The best results in terms of emission intensity and decay time were obtained in the case of 100% glycine excess. The sample with optimum emission characteristics was successfully tested in making glow-in-the-dark coatings applied to two different substrates and using pigment concentrations between 10 and 33% weight.