Multifunctional transparent woods have recently attracted a great interest as efficient products for many applications, such as smart window and smart packaging. Herein, a transparent wood with several desirable properties, including flame-retardant activity, ultraviolet shielding, superhydrophobicity, good roughness, durability and photostability was developed. The current photoluminescent wood showed a remarkable capacity to keep releasing light in the dark for extended durations. Multifunctional transparent wood was prepared by infiltrating a delignified wooden bulk with a combination of polyvinyl alcohol (PVA), ammonium polyphosphate (APP), cellulose nanocrystals, and rare-earth strontium aluminate nanoparticles (RSAN). Cellulose nanocrystals were prepared from microcrystalline cellulose, and used as reinforcement nanofiller to enhance the mechanical strength of the polyvinyl alcohol matrix and a dispersant agent to avoid agglomeration of RSAN. RSAN displayed diameters of 8–16 nm, while cellulose nanocrystals displayed lengths of 75–150 nm and diameters of 5–10 nm. According to photoluminescence spectra and the colorimetric space coordinates reported by the CIE Lab parameters, the transparent wood changed color to bright green when exposed to UV irradiation. For the produced phosphorescent wood surfaces, an absorption band was detected at 365 nm to generate an emission band at 519 nm.