H-1 and C-13 NMR spectroscopy was used to characterize regularly alternating copolymers, poly(amide-enaminonitriles), using 1D and 2D NMR experiments (HMQC and TOSCY) and NMR spectroscopic data of closely related model compounds. Go-polymers from the condensation of an unsymmetric diamine, 4,4＇-diaminobenzanilide, with 1,3- or 1,4-bis(1-chloro-2,2-dicyanovinyl)benzene were determined to be predominately ordered polymers, with similar to 85% of the structures containing head-to-head/tail-to-tail arrangements. The microstructural features of these polymers were determined using 1H NMR spectroscopy where peaks representing head-to-head and tail-to-tail distributions were identified by comparison to a model compound and regularly alternating copolymers that had strictly head-to-head or tail-to-tail compositions.