The spin-probed copolymers of styrene and acrylonitrile differing in monomer content and chain structure were examined by the electron spin resonance (e.s.r.) methods in a wide temperature range. The measurements of spin-lattice relaxation time, T-1(DM), in slow motional region by the double modulation e.s.r. technique reveal two distinct relaxation regions in copolymers and pure polyacrylonitrile matrices. At very low temperatures (region I) a very distinct difference between T-1(DM) values of pure polyacrylonitrile, alternating and statistical copolymers and polystyrene-rich copolymer is ascribed to the effect of packing density of polymer chains. The density modulates the electron spin-lattice relaxation rates and other vibrational modes contributing to the total relaxation rate. At higher temperatures (region II), where the skeleton of a spin probe begins to move, alternating and statistical copolymers of a similar composition show different relaxation rate. The data are reconciled on the basis of the sequence structure of copolymer chains. The difference in glass transition temperature between alternating and statistical copolymers as determined by the e.s.r. measurements reflects local motional heterogeneity as a consequence of chain microstructure. The presence of local motional heterogeneity of a probe near and above the glass transition results from the styrene-rich sequences contributing to the structural heterogeneity in statistical copolymer.