A new vinyl azide monomer, 2-chlorallyl azide (CAA), has been synthesized from commercially available reagent in one step. The reversible addition fragmentation chain transfer (RAFT) copolymerization of CAA with methyl acrylate (MA) was carried out at room temperature using a redox initiator, benzoyl peroxide (BPO)/N,N-dimethylaniline (DMA), in the presence of benzyl 1H-imidazole-1-carbodithioate (BICDT). The polymerization results showed that the process bears the characteristics of controlled/living radical polymerizations, such as the molecular weight increasing linearly with the monomer conversion, the molecular weight distribution being narrow, and a linear relationship existing between In([M](o)/[M]) and the polymerization time. Chain extension polymerization was performed successfully to prepare block copolymer. Furthermore, the azide copolymers were functionalized by Cu-1-catalyzed "click" reaction with alkyne-containing poly(ethylene glycol) (PEG) to yield graft copolymers with hydrophilic PEG side chains. Surface modification of the glass sheet was successfully achieved via the crosslinking reaction of the azide copolymer under UV irradiation at ambient temperature. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1348-1356, 2010