Functional brushes have recently emerged as an extremely versatile way to modify surface properties in a robust and controlled way. In this study, well-defined, high density oligo-N-isopropylacrylamide (oligoNIPAM) brushes with OH and COOH end-groups were fabricated through a reliable strategy by the combination of the self-assembly of bimolecular macroazoinitiator on silicon surface and surface-initiated nitroxide mediated polymerization of N-isopropylacrylamide in the presence of chain transfer agent (i.e., 2-mercaptoethanol or 3-mercaptopropionic acid). The living polymerization produced silicon substrate-coated with functional oligoNIPAM with a target molecular weight and a grafting density as high as 8.14 chains nm2. The functional oligoNIPAM brushes can be employed for the adsorption of biomacromolecules such as DNA and proteins. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013