Abstract The study of metallic multilayers (MM) has presented interesting highlights to understand electrocatalytic properties for organic molecules oxidation. This work reports the preparation and characterization of MM using rhodium or ruthenium as an intermediate layer, Ptpc/Rh/Pt and Ptpc/Ru/Pt, aiming to evaluate the electrocatalytic activity toward methanol and ethanol oxidation in acid medium. For methanol electro-oxidation, the evaluated MM presented higher current density than Ptpc, especially Ptpc/Rh2/Pt1 and Ptpc/Ru5/Pt2, where the increase in peak current density was 283% and 422% compared to Ptpc. By in situ infrared spectroscopy (FTIR in situ), it was observed that in MM the CO2 formation from methanol oxidation occurred in lower potentials compared to Ptpc. In the ethanol oxidation, Ptpc/Rh2/Pt1 and Ptpc/Ru5/Pt2 increase in peak current density 32% and 67% compared to Ptpc, respectively. The bands referring to the acetaldehyde, acetic acid and CO2 were observed first to MM than for Ptpc. The better electroactivity of the metallic multilayers in the electro-oxidation of alcohols could be explained by the changes in the electronic interaction between the exposed platinum surface and the rhodium or ruthenium intermediate layer, which facilitated the oxidation of intermediates at lower potentials, and thus, increasing of the electrocatalytic activity of these materials.