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Spiropyran stimuli-responsive molecule has been applied in various fields, such as data storage, chemical and biological sensing, catalysts, drug transfer and delivery, due to the distinctive absorption characteristics during the structural isomerization. However, most complex molecular design strategies of the spiropyran derivatives limit the application in stimulus-responsive materials. To overcome this difficulty, in this work, a novel photo-chromic molecule (NBG1) was rational designed by linking triphenylamine (TPA) with spiropyran, which exhibited obvious photochromic propertie. Based on this, for the first time, the novel photochromic polysiloxane-based films (Cns) was achieved by using of facile thiol-ene “click” reaction. Cns could realize the fluorescence reversible transformation under Ultraviolet light or heating. Meanwhile, the potential application of NBG1 in anti-counterfeiting has been explored as a double anti-counterfeiting quick response (QR) code. Especially, the convenient approach of constructing photochromic film could be extended to design new stimuli-responsive materials.