Among the most challenging issues in technologies for electrochemical energy conversion are the insufficient activity of the catalysts for the oxygen reduction reaction, catalyst degradation and carbon-support corrosion. In an effort to address these barriers, we aimed towards carbon-free multi/bimetallic materials in the form of mesostructured thin films with tailored physical properties. We present here a new class of metallic materials with tunable near-surface composition, morphology and structure that have led to greatly improved affinity for the electrochemical reduction of oxygen. The level of activity for the oxygen reduction reaction established on mesostructured thin-film catalysts exceeds the highest value reported for bulk polycrystalline Pt bimetallic alloys, and is 20-fold more active than the present state-of-the-art Pt/C nanoscale catalyst.