The copolymers containing N-vinyl-2-pyrrolidone (V) and methyl methacrylate (M) units of different compositions were synthesized by free radical bulk polymerization. The copolymer composition of these copolymers was determined by CHN analysis. The distortionless enhancement by polarization transfer (DEPT) technique was used to resolve the methine, methylene, and methyl resonance signals in the V/M copolymer. Comonomer reactivity ratios were determined by the Kelen-Tudos (KT) and nonlinear least-square error-in-variable (EVM) methods. H-1-C-13 Heteronuclear shift quantum correlation spectroscopy (HSQC) and H-1-H-1 homonuclear total correlation spectroscopy (TOCSY) spectra were used for the resolution of the proton nuclear magnetic resonance (H-1 NMR) spectrum of the V/M copolymers.