A gold-supported, self-assembled monolayer containing imidazole termini provides axial binding sites for the diruthenium cofacial diporphyrins (mu-N-2)Ru-2(DPA)(CH3CN) and (mu-N-2)Ru-2(DPB)(CH3CN). These electrode-bound molecules electrocatalytically reduce dioxygen in a well-characterized environment. The SAM environment makes it easier to study the effect that the eletrode-catalyst interactions are having on the catalysis compared with those of the traditional environment of EPGE.