The acrylonitrile/methyl methacrylate copolymers of different monomer concentration were prepared by photo polymerization using uranyl ion as initiator. The carbon 13 and proton spectra of these copolymers are overlapping and complex. 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 two dimensional C-13-H-1 Heteronuclear Single Quantum Correlation (HSQC) experiments. The methylene, methine and the methyl carbon resonances show both stereochemical (triad level) and compositional (dyad, triad, tetrad, pentad and hexad. level) sensitivity. 2D Double Quantum Filtered Correlated Spectroscopy (DQFCOSY) experiment was used to ascertain the various geminal couplings between the methylene protons.