Chromium tetraaminophthalocyanine (Cr(III)TAPc) has been synthesized and its electrochemical and spectroelectrochemical properties reported. The first reduction and oxidation in this complex occur at the central metal, giving Cr(II)TAPc and Cr(IV)TAPc complexes, respectively, the latter having been observed for the first time. The Cr(III)TAPc species was polymerized onto glassy carbon (GCE) or indium tin oxide (ITO) electrodes and the polymer evolution confirmed by UV/Visible spectroscopy and by scanning electron microscopy. The polymers were employed for the catalytic oxidation of nitrite or nitric oxide, and the catalysis involved the Cr(IV)TAPc(-1) species. (C) 2004 Elsevier B.V. All rights reserved.