The copper(0)-catalyzed living radical polymerization of acrylonitrile (AN) was investigated using ethyl 2-bromoisobutyrate as an initiator and 2,2'-bipyridine as a ligand. The polymerization proceeded smoothly in dimethyl sulphoxide with higher than 90% conversion in 13 h at 25 degrees C. The polymerization kept the features of controlled radical polymerization. H-1 NMR spectra proved that the resultant polymer was end-capped by ethyl 2-bromoisobutyrate species. Such polymerization technique was also successfully introduced to conduct the copolymerization of styrene (St) and AN to obtain well-controlled copolymers of St and AN at 25 degrees C, in which the monomer conversion of St could reach to higher than 90%. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 1183-1189, 2011