Phenolato moieties impart redox flexibility to metal complexes due their accessible (oxidative) redox chemistry and have been proposed as functional ligand moieties in redox non-innocent ligand based transition metal catalysis. Here, the electro-and spectroelectrochemistry of phenolato based mu-oxodiiron(III) complexes [(L-1)Fe(mu-O)Fe(L-1)](2+) (1) and [(L-2)Fe(mu-O)Fe(L-2)]2+ (2), where L-1 = 2-(((di(pyridin-2-yl)methyl)(pyridin-2-ylmethyl)amino)methyl)phenol and L-2 = 3,5-di-tertbuty1-2-(((di(pyridin-2-yemethyl)(pyridin-2-ylmethyeamino)-methyl)phenol, is described. The electrochemical oxidation of 1 in dichloromethane results in aryl C-C coupling of phenoxyl radical ligand moieties to form tetra nuclear complexes, which undergo subsequent oxidation to form iron(III) phenolato based polymers (poly-1). The coupling is blocked by placing test-butyl groups at Para and ortho positions of phenol units (i.e., 2). Poly-1 shows two fully reversible redox processes in monomer free solution. Assignment of species observed during the electrochemical and chemical {(NH4)(2)[Ce-IV(NO3)(6)]} oxidation of 1 in acetonitrile is made by comparison with the UV-vis-NIR absorption and resonance micro-Raman spectroelectrochemistry of poly-1, and by DFT calculations, which confirms that oxidative coupling occurs in acetonitrile also. However, in contrast to that observed in dichloromethane, in acetonitrile, the oligomers formed are degraded in terms of a loss of the Fe(III)-O-Fe(III) bridge by protonation. The oxidative redox behavior of 1 and 2 is, therefore, dominated by the formation and reactivity of Fe(III) bound phenoxyl radicals, which considerably holds implications in regard to the design of phenolato based complexes for oxidation catalysis.