Copolymers of 2-hydroxy ethyl methacrylate and methacrylonitrile (H/M) of different composition were synthesized by free radical bulk polymerization using azobisisobutyronitrile (AIBN) as an initiator under nitrogen atmosphere. The copolymers composition were calculated from H-1 and quantitative C-13{H-1}NMR spectra. The complete spectral assignment of complex and overlapped alpha-methyl and beta-methylene carbon regions in C-13{H-1} NMR spectrum in term of compositional and configurational sequences of H/M copolymers were done with the help of two-dimensional heteronuclear single quantum coherence (HSQC) and total correlation spectroscopy (TOCSY). (c) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 111: 2381-2386, 2009