Bimodal-sized Pt–Sn and Ru–alloy catalysts for the electro-oxidation of ethanol were synthesized using a novel templating approach and evaluated for ethanol oxidation in alkaline media. This templating approach leads to trimodal-sized catalyst particles embedded in and on bimodal-pore carbon support. Electrochemical evaluation suggested that Pt–Sn phases enhance dehydrogenation and/or C–C bond splitting, while Pt–Ru phases facilitates complete oxidation of the intermediate reaction product CO. The criteria for best-performing catalyst are derived from studies and found to be 2–5 nm Pt(Sn) and the addition of Ru is conjectured to be beneficial. Mass transport effects observed demonstrates that it is possible to effect catalytic performance using the hierarchically structured templating approach used.