The present paper focuses on the development of novel smart fabrics having warning photoluminescent properties that keep light emitting for a period of time in the absence of an illumination source. Phosphorescence commonly brings added value for safety enhancement. Herein, we introduce a textile material coated with a photoluminescent layer. Dysprosium- and europium-doped strontium aluminate phosphor were admixed with a mixture of an adhesive binder and distilled water to afford the pigment binder formula which was then applied directly onto wool fabric using a spray-coating technique. Results indicated that the optimal excitation wavelength of the coated fabric occurred at 365 nm, and an emission peak was also observed at 517 nm. A homogeneous phosphorescent layer was assembled on the surface of the wool fabric relying on the pigment concentration existing in the pigment-binder formula. This coated layer represents a substantial development of greenish-yellow, bright white, turquoise, and off-white colors as described by the CIE Lab color space data under ultraviolet irradiation. The decay curves and lifetime of phosphorescence were investigated. The fluorescent optical microscopy results, energy dispersive X-ray analysis, photoluminescence spectroscopic data, scanning electron microscopy images, and elemental mapping are described. The comfort properties of treated wool fabrics were evaluated by studying their stiffness and air permeability.