Copolymers containing N-vinylcarbazole (V) and butyl methacrylate (B) units of different compositions were synthesized and their compositions were determined from quantitative 13C{ 1H} NMR spectroscopy. The reactivity ratios of the comonomers were estimated using the Kelen–Tudos and non-linear error in variable methods. The complete spectral assignment in terms of compositional and configurational sequences of the overlapping 1H and 13C{ 1H} spectra of the copolymers were done with the help of distortionless enhancement by polarization transfer, 2D heteronuclear single quantum correlation and total correlated spectroscopy experiments.