The in situ photopolymerization hydrogen-bonded molecular macroclusters of N-isopropylacrylamide (NIPAAm) formed on silica surfaces in chloroform was performed for generating polymeric nano-films. The ATR-FTIR spectra showed that the structure of NIPAAm underwent a transformation from trans- to cis-stereoisomer during polymerization. Changes in the contact angle at temperatures below and above the lower critical solution temperature (LCST) were observed at 35degrees and 62degrees, respectively.