trans-4-Acryloyloxyazobenzene/vinylidene chloride (A/V) copolymers of different monomer concentrations were prepared by solution polymerization using benzoyl peroxide as initiator. The copolymer composition was determined from the quantitative 13C{1H} NMR spectrum. The carbonyl carbon of A- and the quaternary carbon of V-centered resonances were used for determining the sequences in terms of the distribution of A- and V-centered triads. The sequence distribution of A- and V-centered triads determined from 13C{1H} NMR spectrum of the copolymer is in good agreement with triad concentration calculated from statistical model. The comonomer reactivity ratios, determined by both Kelen–Tüdos (KT) and nonlinear error in variables (EVM) method are rA=0.36±0.03, rV=1.02±0.06; rA=0.37 and rV=1.04, respectively. 13C Distortionless enhancement by polarization transfer (DEPT) spectrum was used to differentiate the resonance signals of methine (A) and methylene carbon signals of A- and V-units. Assignments to the methine and methylene resonance signals have been assigned up to the tetrad levels using 2D HSQC experiments. The geminal coupling in the methylene and methine proton region is shown in the 2D TOCSY spectrum.