2-Hydroxyethyl acrylamide was successfully polymerized via single-electron transfer initiation on the silicon surface and propagation through the reversible addition-fragmentation chain transfer (SET-RAFT) polymerization at ambient temperature for different polymerization times. This work is the first time application of the surface-initiated SET-RAFT mechanism to afford the preparation of well-defined poly(2-hydroxyethyl acrylamide) [poly(HEAAm)] brushes at ambient temperature. The polymerization was well controlled and produced poly(HEAAm) brushes on the silicon surface with a well-defined target molecular weight. The controlled nature of the polymerization was further demonstrated in the presence of sulfur atoms at the chain ends in X-ray photoelectron spectroscopy experiments. The grafting density (sigma, chains nm(-2)) and the average distance between grafting points (D, nm) were found to be 0.42 chains nm(-2) and 1.74nm, respectively, indicating moderate grafting density. (c) 2019 Wiley Periodicals, Inc.