Poly(styrene-eo-vinylidene chloride) (SN) copolymers were prepared by free-radical photopolymerization using uranyl nitrate as an initiator. The microstructure of the copolymer SN was investigated by H-1- and C-13(H-1)-NMR, H-1-C-13-heteronuclear shift quantum correlation (HSQC) NMR, and homonuclear total correlated spectroscopy (TOCSY). The H-1-NMR spectra of the copolymers is complex due to overlapping resonance signals of the various triad configurations. Assignments were made up to the triad and tetrad levels for the methylene and methine regions using two-dimensional HSQC experiments. A C-13-distortionless enhancement by polarization transfer (DEPT) spectrum was used to differentiate between the carbon resonance signals of methine and the methylene units. The geminal couplings in the methylene protons and vicinal coupling between the methine and methylene protons were detected from the TOCSY spectra. Monte Carlo simulations were used to investigate the affect of the degree of polymerization on the triad fractions.