Considering the increasing energy consumption in urban lighting systems and the need for developing sustainable solutions, the use of photoluminescent materials has attracted attention as a novel option in urban infrastructure. However, incorporating these materials throughout the entire volume of concrete may increase costs and reduce some mechanical properties. In this study, with the aim of reducing the consumption of photoluminescent materials and preventing the deterioration of concrete mechanical properties, the approach of transferring the photoluminescent material from the concrete bulk to a surface coating layer has been investigated. In this research, a photoluminescent coating containing CaAl₂O₄ powder within epoxy and polyurethane polymer resin matrices has been prepared and applied to the concrete surface with an approximate thickness of 3±1 mm. The volumetric ratio of CaAl₂O₄ in the coatings has been adjusted to 0, 25, 50, 75, and 100%, and their performance has been evaluated under different environmental conditions. To assess the performance of the coatings, abrasion, acidic environment, freeze–thaw cycles, and thermal stability tests have been conducted, and the adhesion strength of the coating to concrete has been determined using the Pull-Off test according to ASTM C1583. The results have shown that the epoxy-based coating has exhibited better performance than the polyurethane coating. The abrasion durability of sample E 100% has increased by 333% compared with sample O 100%. The resistance in an acidic environment has been reported to be 17% higher in the epoxy coating than in the polyurethane coating. The resistance under freeze–thaw cycles has also shown an increase of 22%. In addition, the thermal stability of the epoxy coating at 350 °C has been about 21% higher than that of polyurethane. However, at 700 °C both systems have experienced complete burning and loss of strength. The results have indicated that the use of epoxy based photoluminescent coatings can improve the durability and performance of such coatings under various environmental conditions.