A simple method of preparing stimuli-responsive polystyrene (PS)/polycaprolactone (PCL) nanolayered films with by growing poly(N-isopropylacrylamide) (PNIPAM) brush on the surface by surface-initiated polymerization is reported. Atom transfer radical polymerization (ATRP) initiator with a benzophenone moiety is attached onto the surface by UV irradiation. After ATRP polymerization, PNIPAM brush films with varying thicknesses are produced. X-ray photoelectron spectroscopy (XPS) confirms the successful deposition of initiator and grafting of the polymer. Moreover, the behavior of the brush film as a function of temperature is demonstrated by contact angle experiments. Photopatterning is also achieved by using a photomask and is confirmed by Fourier Transform Infrared (FTIR) imaging.