The synthesis and the study of the spectroscopic and electrochemical properties as well as the solution behavior of the novel 2-ferrocenyl-2,4-dihydro-1H-3,1-benzoxazine (1a) are described. NMR studies reveal the existence of a tautomeric equilibria between the cyclic (1a) and the open-chain form (2a). Electrochemical studies based on cyclic voltametry and 57Fe Mossbauer spectroscopy as well as a comparative study of the ring-chain tautomerism of 1a and that of 2-phenyl-2,4-dihydro-1H-3,1-benzoxazine (3a) are also reported.