Electrochemical behavior and superoxide-assisted electrochemical deposition of Mn(III)chloride 5,10,15,20-tetrakis(meta-aminophenyl)porphine (MnCIT(m-NH2Ph)P) and Mn(III)chloride 5,10,15,20-tetrakis(para-aminophenyl)porphine (MnCIT(p-NH2Ph)P) in DMSO solutions on electrodes of various types have been investigated. It is shown that a surface film is formed in the oxygen electroreduction potentials region. The influence of the amino group position in the phenyl substituent on the deposition kinetics of the film and its morphology is demonstrated. It has been shown that the main motif of the porphyrin-porphyrin bond is phenazine type bridges, if the aminophenyl-porphyrin film is deposited by the developed method. A mechanism has been proposed for forming these bridges for the case of superoxide-assisted electrochemical deposition of poly-Mn-aminophenyl porphyrins films. It has been established that polyporphyrin films obtained from solutions of MnCIT(m-NH2Ph)P and MnCIT(p-NH2Ph)P in DMSO are electrocatalytically active in the reaction of oxygen electroreduction in an alkaline medium. (C) 2018 Elsevier Ltd. All rights reserved.