Multifunctional photochromic and fluorescent woods that can change their color in the presence of ultraviolet light were developed. A formulation of electrospun glass nanofibers-reinforced styrene as a hosting agent and rare-earth strontium aluminate (RSA) as a photoluminescent was infiltrated into a lignin-modified wooden substrate, resulting in translucent wood with fluorescence and photochromic properties. The RSA pigment is known for its good photostability and thermal stability. An ideal method for producing transparent photoluminescent wood involves dispersing the RSA phosphor in pre-polymerized glass nanofibers-reinforced styrene without aggregation. According to the colorimetric data from the CIE (Commission Internationale de l´Eclairage) Lab color space coordinates, this photoluminescent wood substrate became green when exposed to ultraviolet light, but remained colorless when exposed to visible light. Electron microscopic images were used to investigate the morphologies of the synthesized pigment nanoparticles (NPs) and electrospun glass nanofibers, displaying diameters of 5–15 nm and 50–100 nm, respectively. The photoluminescent woods were inspected with different microscopic and spectroscopic techniques, including energy-dispersive X-ray spectroscopy (EDX), X-ray fluorescent spectroscopy (XRF), and scanning electron microscopy (SEM). Upon excitation at 365 nm, the photoluminescence transparent timbers demonstrated an emission intensity at 519 nm. When increase the phosphor content, the produced luminous wood was monitored to be more water-resistant and had better protection from ultraviolet rays. The reaction of the transparent luminous wood to ultraviolet light was rapid and reversible without fatigue.