Oxygen reduction reaction (ORR) by decamethylferrocene (DMFc) at a water/1,2-dichloroethane (DCE) interface proceeds as a proton coupled electron transfer process, with the supply of protons by the aqueous phase and electrons by the electron donor DMFc in the organic phase. In the present work, the reduction of oxygen by DMFc has been investigated in the presence of different aniline derivatives such as 3,5,N,N-Tetramethylaniline (TMA), N,N-Diethylaniline (DEA), 4-Nitroaniline (4-NA), 4-Dodecylaniline (4-DA) which act as proton ionophores to transfer protons from the aqueous to the organic phase. It has been found that ORR by DMFc can be catalyzed efficiently by the use of aniline derivatives depending on their basicity strength which follows an order of DEA > TMA > 4-DA > 4- NA. © 2012 Elsevier B.V. All rights reserved.