Smart photoresponsive structured films with tunable wettability and ambient humidity were developed from acrylamino spiropyran-methyl methacrylate copolymer by electrospinning in this work. The wettability of the electrospun materials and ambient humidity can be reversibly regulated by the simple change of UV-Vis light irradiation due to the photoisomerization mechanism of spiropyran chromophore. Under UV light irradiation, the spiropyran molecules exhibit a colored polar open-ring status which is hydrophilic, whereas under visible light irradiation it is colorless, nonpolar, and hydrophobic. As a promising and efficient method to produce surfaces with appropriate roughness, electrospinning was used to control the morphology of the copolymer surface, and significantly it is found that the roughness of the surface can strongly influence the reversible variation range of the water contact angle and humidity. POLYM. ENG. SCI., 59:E279-E286, 2019. (c) 2018 Society of Plastics Engineers