The microstructure of poly(trans-4-acryloyloxyazobenzene) P(AB) homopolymer, prepared by solution polymerization using AlBN as initiator is analysed by one- and two-dimensional NMR spectrotcopy. Sequence distribution was calculated from 1 3 C{ 1 H}n.m.r. spectrum of the homopolymer. A 1 3 C distortionless enhancement by polarization transfer spectrum was used to differentiate between the resonance signals of methine and methylene units in the homopolymer. The triad sequence distribution of poly(trans-4-acryloyloxyazobenzene) P(AB), determined from carbonyl resonance of the homopolymer, is in good agreement with the triad concentrations calculated from the Bernoullian statistical model. 2D heteronuclear single quantum correlation (HSQC) and correlated spectroscopy (COSY) spectroscopy was used to analyse the complex 1 Hn.m.r. spectrum. Homonuclear 2D TOCSY n.m.r. spectroscopy was used to ascertain the various configurational sequence of the poly(trans-4-acryloyloxyazobenzene) P(AB) homopolymer. 2D NOESY experiment was carried out to determine one of the many probable conformations of the homopolymer in solution state.