In this work, an electropolymerization of the [(FeTPC)-T-II](2+) macrocyclic complex occurring upon the electroreduction of dioxygen in dry acetonitrile is reported, TPC = N,N’,N’-tri-2-picolyl-1,4,7-triazacy clononane. It is shown that oxy radicals, such as superoxide (O-2(.-)) and hydroxyl radical (OH.), were able to initiate the iron chelate polymerization at the surface of glassy carbon (GC) and silver electrode. Structural studies on the polymer morphology were performed using surface-enhanced Raman scattering (SERS) on a silver electrode and the repetitive cyclic voltammetry at GC. The voltammetric studies revealed that bipicolyl units were involved in the polymer structure. On the other hand, the resonance Raman spectroscopic investigations exhibited frequency and intensity dispersions of the poly[(FeTPC)-T-II](2+) Raman bands with the excitation wavelength. At lambda(ex) = 647.1 nm, the new Raman bands were developed at v = 1148, 1270, 1384, 1443, and 1511 cm(-1) with respect to those recorded for the parent [(FeTPC)-T-II](2+) monomer. These vibrational modes were assigned to an excited "quinoid" state of the polymer. In conclusion, the electropolymerization of the [(FeTPC)-T-II](2+) complex was considered in terms of a 2-picoline ring-coupling mechanism.