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• Porphyrins with different number of electroactive substituents. • Effect of porphyrin structure on the film formation and film properties. • Mechanism and kinetic of oxygen electroreduction on the films. • Difference in films morphology, activity and, probable, in catalytic site density. The paper analyzes how the structure of porphyrin affects its electrochemical characteristics, film formation process and physicochemical properties of the obtained materials. A comparison of the redox processes of 21H,23H-5,15-bis-(4-aminophenyl)-10,20-di-phenyl porphyrin (Porph I) and 21H,23H-5,10,15-tris-(4-aminophenyl)-20-phenyl porphyrin (Porph II) shows that Porph I is more stable in oxidation and less stable in reduction processes than Porph II. The presence of electrochemically active amino groups in the composition of the porphyrin molecules allows the superoxide-assisted electrochemical deposition method to be applied to successfully form poly-Porph I and poly-Porph II films from dimethyl sulfoxide solutions. Spectral methods confirm that the obtained materials preserve their porphyrin structure. The structure of the initial monomer molecules is demonstrated to affect the film formation and surface morphology of the prepared materials. Oxygen electroreduction in an alkaline medium is shown to have smaller kinetic limitations on poly-Porph II films than that on poly-Porph I ones. [ABSTRACT FROM AUTHOR]