Terpolymers of acrylonitrile (A), methyl methacrylate (B), and methyl acrylate (M) were synthesized under optimized atom transfer radical polymerization conditions using 2-bromopropionitrile as an initiator and CuBr/dinonyl bipyridine as a catalyst. Variation of the feed composition led to terpolymers with different compositions. Composition of synthesized terpolymers were calculated from quantitative C-13(H-1)) NMR spectra. Number average molecular weight and polydispersity index were determined by gel permeation chromatography. The overlapping and broad signals of the terpolymers were assigned completely to various compositional and configurational sequences by correlation of one-dimensional H-1, C-13{H-1}), and distortionless enhancement by polarization transfer and two-dimensional heteronuclear single quantum coherence (HSQC) and total correlation spectroscopy (TOCSY). 2D HSQC NMR study shows one to one correlation between carbon and proton signals, while 2D TOCSY spectra were used to confirm 1, 2 bond geminal couplings between non-equivalent protons of same methylene group. (c) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 25-37, 2009