In recent decades, research on persistent luminescence has led to new phosphors and promising performances. Efforts to improve the quality of phosphors’ afterglow have paved the way toward innovative solutions for many disciplines. However, there are few examples of the implementation of luminescent materials. In addition to providing a general background on persistent luminescence, the techniques used for its analysis, and its multidisciplinary potential in energy and environmental science, this article aims to explain the existing gap between the physical-chemical approach and the effective implementation of luminescent materials in larger-scale applications. It investigates engineering solutions in terms of the possible benefits of luminescence in lighting energy savings and passive cooling of urban surfaces. Finally, this article aims to reduce the abovementioned gap by suggesting what is most needed for the successful application of luminescent materials in the built environment.