Oxygen reduction reaction (ORR) electrodes play an important role in the development of new battery and fuel cell technologies. However most of the presented electrode materials cannot provide the efficiency required for these applications, and/or they are based on economically unfavourable noble metals. In this article, multi-layer electrodes of high conductivity PEDOT prepared by vacuum vapour phase polymerization in the presence of a PEG–PPG–PEG triblock copolymer are used to fabricate a metal-free oxygen reduction electrode. After optimizing the main production parameters, measuring ORR performance of the metal-free PEDOT based electrodes confirms that they have the ability to deliver a stable electrocatalytic activity. A chemical treatment is also used for further enhancing the electrocatalytic activity of these electrodes. Depending on pH, the electrocatalytic activity of these treated electrodes reaches a higher or the same level as platinum based electrodes.