This work addresses the influence of amine group substituted at para and ortho positions of the phenyl groups on the electrochemical and electrocatalytic properties of cobalt porphyrins self-assembled on glassy carbon electrode (GCE). We have synthesized meso-tetra(para-aminophenyl) porphyrinatocobalt(II) (Co(II)MTpAP) and meso-tetra(ortho-aminophenyl)porphyrinatocobalt(II) (Co(II)MToAP) and were self-assembled on GCE through Michael addition of nucleophilic amine with olefinic GCE surface. Cyclic voltammetry, reflectance spectroscopy and X-ray photoelectron spectroscopy (XPS) techniques were employed to confirm the formation of the self-assembled monolayers (SAMs) of Co(II)MTpAP and Co(II)MToAP on GCEs. Interestingly, the SAM of Co(II)MTpAP in 0.1 M H2SO4 shows two redox waves at 0.37 and 0.60V whereas the SAM of Co(II)MToAP shows a single redox wave at 0.32V, indicating the influence of amine group position in the phenyl ring on the redox chemistry of porphyrin. In contrary, the SAMs of the corresponding free base porphyrins prepared under identical conditions show a single redox wave around 0.36V. Thus, we have assigned the redox wave at 0.37V to Co(II)Por(1-)/Co(II)Por(2-) and 0.60V to Co-III/II redox couples for the SAM of Co(II)MTpAP. In the case of Co(II)MToAP, we have assigned the redox wave at 0.32 V due to both Co(II)Por(1-)/Co(II)Por(2-) and Coals. The surface coverage estimated from the charge consumed for the oxidation of Co-III/II was used to study the thermodynamics and kinetics of Co(II)MTpAP and Co(II)MToAP self-assembled on GCE. Further, the electrochemical reduction of dioxygen was studied at the SAMs of Co(II)MTpAP and Co(II)MToAP in 0.1 M H2SO4. The dioxygen reduction potential was shifted to less positive potential with enhanced current at both the SAMs of Co(II)MTpAP and Co(II)MToAP when compared to bare GCE. Among the two SAMs, Co(II)MTpAP significantly reduced the overpotential of dioxygen reduction (65 mV) when compared to Co(II)MToAP. (C) 2013 Elsevier Ltd. All rights reserved.