Copolymerization of acrylonitrile and ethyl methacrylate using atom transfer radical polymerization (ATRP) at ambient temperature was carried out under optimized reaction conditions using 2-bromopropionitrile as initiator and CuBr/2,2'-bipyridine as the catalyst system. The copolymer composition, obtained from H-1 NMR spectra, were used to determine the monomer reactivity ratios (r(A) = 0.68 and r(E) = 1.75) involved in ATRP Two-dimensional NMR (heteronuclear single quantum correlation and total correlated spectroscopy) experiments were employed to resolve the highly overlapping and complex H-1 and C-13{H-1} NMR spectra of copolymers. The complete spectral assignments of the quaternary carbons viz. carbonyl and nitrile carbons were done with the help of heteronuclear multiple bond correlation spectra. (c) 2006 Wiley Periodicals, Inc.