4-Vinyl pyridine-methacrylonitrile (V/M) copolymers of different composition were prepared by bulk polymerization using benzoyl peroxide as an initiator. The copolymer composition was determined from quantitative C-13{H}-NMR spectra. The reactivity ratios for V/M copolymer obtained from a linear Kelen-Tudos method (KT) and nonlinear error-in-variables method (EVM) are r(V)=0.79+/-0.12, r(M)=0.38+/-0.09 and r(V)=0.79+/-0.13, r(M)=0.38+/-0.07, respectively. The complete spectral assignment in term of compositional and configurational sequences of these copolymers were done with the help of distortionless enhancement by polarization transfer (DEPT), two-dimensional heteronuclear single quantum coherence spectroscopy (HSQC). Total correlated spectroscopy (TOCSY) experiment was used to assign the various three-bond H-1-H-1 couplings in the V/M copolymer. (C) 2003 Wiley Periodicals, Inc.