The electrochemical and spectroelectrochemical characterization of two water-soluble porphyrins, namely the tetrachloro salt of cobalt(II) tetrakis-(N-methyl pyridyl)-b-octabromoporphyrin, [(Br 8 TMPyP)Co II ]Cl 4 , and the tetrasodium salt of cobalt(II) tetrakis-(4-sulfonatophenyl)-b-octabromoporphyrin, Na 4 [(Br 8 TPPS)Co II ], under different pH conditions is reported. The investigated porphyrins are highly non-planar and electron-deficient owing to the presence of eight bromides at the b-pyrrole positions and the four meso-aryl substituents. The redox potentials corresponding to the first oxidation and first reduction are shifted positively compared with the redox potentials of the respective unbrominated porphyrin derivatives. Spectroelectrochemical studies reveal the formation of a cobalt(III) complex during the first oxidation of both cobalt porphyrins. The first reduction of [(Br 8 TPPS)Co II ] 4À results in a cobalt(I) complex, while involvement of the peripheral N-methyl pyridyl groups in the case of [(Br 8 TMPyP)Co II ] 4 is suggested. The peak potentials of the first oxidation corresponding to a Co II /Co III redox couple of both investigated compounds are found to be pH-dependent. Debromination of the b-pyrrole bromo substituents of [(Br 8 TMPyP)Co II ] 4 at more negative potentials is observed. The UV-vis spectrum obtained after bulk electrolysis of [(Br 8 TMPyP)Co II ] 4 at À1.0 V vs Ag/AgCl followed by reoxidation at 0.2 V indicates complete elimination of the bromo substituents of the porphyrin periphery.