Vinyl benzene methyl acrylic ester copolymerization was achieved using controlled radical polymerization (CRP). The reaction was carried out by using methyl 2-bromopropionate (C4H7BrO2) initiator under catalytic conditions employing CuBr/N,N,N',N',N''-pentamethyldiethylenetriamine. The GPC-gel permeation chromatography method has been employed to ascertain distribution of molecular mass. Copolymer composition was determined through proton NMR analysis. Both nonlinear error-in-variables (EVM) and Kelen-Tudos (KT) methods were used to obtain the comonomer reactivity ratios respectively as rS =1.09, 1.09 ± 0.05 and rM= 0.36, 0.35 ± 0.17. The resonance frequency pertaining to both quaternary carbons present in styrene as well as those pertaining to carbonylic carbons present in methyl acrylate segment have been observed to be dependent on the sequence and were identified up to the triad level. The proton (1H) and carbon-13 (13C) NMR spectroscopy was used to fully assign the peaks in the copolymers using analytical techniques such as DEPT-distortionless enhancement by polarization transfer, as well as 2D NMR methods.