Various reports demonstrated that azobenzene derivatives are the chromophore of choice in photoresponsive surfaces showing reversible surface polarity. Hitherto the surface study of coating films based on polymer/azobenzene blends using contact angle measurements remained unexplored. To provide insight into the surface polarity of polymer/dye blend films, poly(methyl methacrylate) (PMMA) blends containing photoresponsive 4-hydroxy-4′-methylazobenzene (AZO1) and 4,4′-dimethylazobenzene (AZO2) as coating films on clear glass substrates are investigated in this work. Contact angle measurements were carried out to unravel the role of substituents in the surface polarity and the orientation of chromophores in the coating matrices before and after UV light (λ_max = 365 nm) irradiation. Changes in water contact angles measured on the PMMA/azobenzene coating films indicated that the surface polarity is reversible as the chromophores underwent reversible trans–cis isomerisation. It has been revealed that the repeated trans–cis isomerisation led to the random reorientation and arrangement of chromophores in PMMA/AZO1 coating films. Then, to indicate the possibility of the disruption of interfacial interactions due to the repeated trans–cis isomerisation processes, as a proof of concept experiment, it is shown that the commercial acrylic-based pressure-sensitive sticker which adhered strongly to the PMMA/AZO1(13) coating film is peeled off from the coating surface after being subjected to a cycle of UV light irradiation for 12 hours, followed by dark conditions for another 12 hours within 14 days. The proof of concept study will lead to more development of smart photoresponsive coating films using simple polymer/dye blends.