Copolymers of 2-Hydroxy ethyl methacrylate and methyl acrylate (H/M) of different compositions were synthesized by free radical bulk polymerization using azobisisobutyronitrile (AIBN) as an initiator under nitrogen atmosphere. The copolymers compositions were calculated from 1 H NMR spectra. The reactivity ratios for H/M copolymers obtained from a linear Kelen–Tudos method (KT) and nonlinear error-in-variables method (EVM) are r H =3.31±0.08, r M =0.23±0.00 and r H =3.32, r M =0.23, respectively. The complete spectral assignment of methine, methylene, methyl and carbonyl carbon regions in terms of compositional and configurational sequences of H/M copolymers was done with the help of 13 C{ 1 H} NMR, distortionless enhancement by polarization transfer (DEPT), two-dimensional heteronuclear single quantum coherence (HSQC) along with total correlated spectroscopy (TOCSY). Further, the assignments of carbonyl region were made with the help of heteronuclear multiple bond coherence (HMBC) spectrum.