The microstructure of trans-3-methacryloyloxyazobenzene-methyl methacrylate copolymers prepared by solution polymerization process using AIBN as initiator is analyzed by one-and two-dimensional spectroscopy. Sequence distribution was calculated from the C-13(H-1)-NMR spectra of the copolymers. Comonomer reactivity ratios were determined using the Kelen-Tudos and the nonlinear error-in-variables methods are r(A) = 1.14 +/- 0.08 and r(M) = 0.51 +/- 0.03; r(A) = 1.13 +/- 0.1 and r(M) = 0.50 +/- 0.04, respectively. The sequence distribution of A- and M-centered triads determined from C-13(H-1)-NMR spectra of copolymer is in good agreement with triad concentration calculated from a statistical model. The 2-D heteronuclear single-quantum correlation and correlated spectroscopy (TOCSY) was used to analyze the complex H-1-NMR spectrum.