The objective of the current study is to develop novel photochromic polyurethane (PUR) nanofibrous films supported with cellulose nanowhiskers (CNW) and immobilized with nanoparticles of alkaline‐earth doped aluminate (NAEA) using the highly efficient and low‐cost solution blowing spinning (SBS) technique. CNW revealed a crystal diameter of 4–8 nm, and a crystal length of 55–105 nm. The solution blown spun nanofibers exhibited diameters of 250–450 nm. In order to prepare a transparent film, CNW and NAEA must be dispersed efficiently in the PUR composite. When supported with CNW, the efficiency of PUR nanofibrous films was strengthened. Cellulose paper sheets were coated with the colorless NAEA/CNW@PUR films to emit a green light at 518 nm upon excitation at 365 nm as proved by photoluminescence spectra. The prepared nanofibrous films exhibited efficient optical photochromic characteristics for potential security encoding applications. The nanofibers‐coated papers showed high photochromic reversibility without fatigue. The current approach can be reported as an efficient technology for authentication of commercial products.