The photoresponsive polyhedral oligomeric silsesquioxanes (POSS) based fluorinated azobenzene‐containing polymers were prepared and characterized by NMR, FT‐IR, GPC, XRD, TG and UV–Vis spectra. The thermal property of the polymers was improved by the introduction of POSS cage. The trans‐cis photoisomerization of the polymers in solution was similar to that of the fluorinated azobenzene monomer and in accordance with the first‐order reaction kinetics equation within the first 250 seconds UV irradiation. The cotton fabrics coated with the polymers showed excellent water repellency and possessed switchable wettability under UV irradiation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43540.

Photoresponsive POSS-based polymers were successfully prepared via radical polymerization. The surface wettability of both water and oil on the polymers coated fabrics can be intelligently controlled by applying irradiation with UV or visible light.