In this work, Cu(0)-mediated radical copolymerization of vinyl acetate (VAc) and acrylonitrile (AN) was explored. The polymerization was carried out at 25 degrees C with 2,2'-bipyridine as ligand and dimethyl sulfoxide as solvent. The copolymerization proceeded smoothly producing moderately controlled molecular weights at low VAc feed ratios. The high VAc feed ratios generated low polymerization rate and poorly controlled molecular weights. FTIR, H-1 NMR, and differential scanning calorimetry confirmed the successful obtaining of the copolymers. Based on H-1 NMR spectra, the reactivity ratios of VAc and AN were calculated to be 0.003 and 1.605, respectively. This work conveyed the first example for the Cu(0)-mediated radical polymerization of AN and VAc, wherein VAc cannot be homopolymerized by Cu(0)-mediated radical polymerization technique. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: 4983-4989, 2012