Acrylonitrile-Styrene (A/S) copolymers were prepared by photopolymerization using uranyl nitrate ion as initiator. The copolymer compositions were determined by elemental analysis, and comonomer reactivity ratios were determined by nonlinear least squares error in variables method (EVM). The complete spectral assignment of the C-13 and H-1-NMR spectra were done with the help of Distortionless Enhancement by Polarization Transfer (DEPT) and by the two dimensional C-13-H-1 Heteronuclear Single Quantum Correlation (HSQC) and TOCSY experiments. The methylene and methine carbon resonance show both stereochemical and compositional sensitivity. The 2-D Total Correlated Spectroscopy (TOCSY) experiment was used to ascertain the Various geminal coupling between the methylene protons.