CoN4 complexes like Co phthalocyanines (CoPc) have been extensively studied as electrocatalysts for the oxygen reduction reaction (ORR) but they only promote the 2-electron reduction of O₂ to give peroxide. In contrast, vitamin B₁₂ a Co macrocyclic naturally occurring molecule has attracted the attention of the scientific community because instead of catalysing the 2-electron reduction of O₂ to H₂O₂ like the other Co macrocycles it promotes the 4-electron reduction to H₂O. Vitamin B₁₂ possesses an axial back ligand and this seems to be the reason for its higher activity and selectivity for the 4-electron reduction of O₂. To test this hypothesis, we synthetized a CoPc axially coordinated to pyridine anchored to carbon nano-tubes (CoPc-Py-CNT). The Co centre is therefore coordinated to 5 N as in vitamin B₁₂. The modified CoPc containing catalytic material was characterized by EPR and XPS spectroscopy. Ab initio calculations, Koutecky– Levich extrapolation and Tafel plots well describe the similarities between the 2 complexes and reveal insights into the mechanism of action of Co penta-coordinated complexes. According to our results the pyridine back ligand increases the Co-O₂ binding energy and making it more similar to that of Vitamin B₁₂, favouring the splitting of the O-O bond. The back ligand then plays a crucial role in modifying Co-O₂ binding energy which is a well know reactivity descriptor.