The oxygen reduction reaction (ORR) is one of the key processes for electrochemical energy storage, such as the cathode process in fuel cells and metal–air batteries. To date, the efficiency of the ORR half-reaction limits the overall performance of these energy storage devices. Traditional platinum-based materials are expensive and cannot provide the desired ORR efficiency. As an alternative, a new catalytic scheme for an ORR was proposed, which consisted of an electrode modified with a TEMPO-containing conductive polymer and a solution redox mediator system based on nitrogen oxides (NOx). NOx is perfect for oxygen reduction in solution, which, however, cannot be efficiently reduced onto a pristine electrode, while TEMPO is inactive in the ORR itself but catalyzes the electrochemical reduction of NO2 on the electrode surface. Together, these catalysts have a synergistic effect, enabling an efficient ORR in an acidic medium. In the present study, the synthesis of a novel TEMPO-containing conductive polymer and its application in the synergistic ORR system with a NOx mediator is described. The proposed mediator system may increase the performance of proton-exchange fuel cells and metal–air batteries.