The electrocatalytic activity of thin, metal‐containing polymer films was studied. The films were prepared on glassy carbon electrodes in a glow‐discharge which was established in mixtures of acrylonitrile and metal acetylacetonate vapors at 300°C. The produced films were electronically conductive and solution permeable. It is proposed that electrochemical reactions can proceed not only on the surface but also inside these films at the active sites formed by the incorporated metal. The cathodic dioxygen reduction in acidic and alkaline electrolytes was used as a test reaction for the electrocatalytic activity and stability of the electrodes.