Abstract The paper discusses the synthesis of the N,N,′-azobis(formamidopropionic) acid (AFP), along with some characteristics determined from NMR spectrum, differential thermal analysis, and DSC. The behavior of AFP acid—as well as of its analogue, N,N′-azobis(formamidoacetic) acid (AFA)—has been studied in the reaction with aromatic diamine and with bis(glycol)terephthalate, leading to azopolymers of the azopolyamide, or azopolyester, type. On employing N,N′-bis(β-hydroxyethyl) azobis-formamide (HEAF) as the azo bifunctional compound in the reaction with diphenylmethane diisocyanate, a polyurethane possessing azo groups was obtained. The structure of the azopolymers has been spectroscopically confirmed.