The microstructure of vinylidene chloride-methyl acrylate copolymers prepared by a photopolymerization process using uranyl ion as photosensitizer is analyzed by one- and two-dimensional NMR spectroscopy. Sequence distribution was calculated from C-13{H-1} NMR spectra of the copolymers. A C-13 distortionless enhancement by polarization transfer spectrum was used to differentiate between the resonance signals of methoxy and methylene units in the copolymer. Comonomer reactivity ratios were determined using Kelen-Tudos and the nonlinear error in variables methods. The sequence distribution of vinylidene chloride- and methyl acrylate-centered triads determined from C-13{H} NMR spectra of copolymers is in good agreement with triad concentrations calculated from statistical model and Monte Carlo simulation methods. 2D heteronuclear single quantum correlation and correlated spectroscopy spectrum was used to analyze the complex H-1 NMR spectrum.