Multilayered polymer systems produced by multilayer coextrusion have a variety of applications as gas barrier films, packaging and optical applications. Surface modification with polymers is commonly accomplished via the free radical process but offers poor controllability over the brush length. This disadvantage can be overcome by the use of controlled living polymerization, such as atom transfer radical polymerization (ATRP). Stimuli-responsive surfaces allow the membranes to change their structural, charge or affinity by manipulation of environmental conditions. Such membranes could be potentially used for the development of novel multi-component separation protocols with tunable surfaces. The proposed method involves the synthesis of an ATRP initiator with a benzophenone moiety. Benzophenone is well known for its photo reactivity in a wide range of chemical environments. The fabrication process was generally based on spin coating or dip coating of the multilayer film. The stimuli-responsive polymer, poly(N-isopropylacrylamide) (PNIPAM), on the membrane film is grown by surface initiated polymerization (SIP) technique. This technique has the benefit of placing initiating groups directly on the surface which allows for good control over the grafting process. This technique can be expanded to photopatterning with applications in different areas such as biomaterials, and microelectromechanical devices. Common patterning strategies such as microcontact printing, electron beam lithography, photoetching, and electro-oxidation method require lengthy and expensive steps. X-ray photoelectron spectroscopy (XPS) confirmed the successful deposition of the initiator and grafting of the polymer. Moreover, the behavior of the brush film as a function of temperature was demonstrated by contact angle experiments.