Electrochemical impedance spectroscopy (EIS) along with cyclic voltammetry (CV) has been applied as a tool for the mechanistic investigation of methanol oxidation on nanoparticulate PtRu fuel cell anodes of a commercially available state of the art membrane electrode assembly (MEA). The spectra could be fitted to a circuit derived analytically for multi-step single adsorbed intermediate reactions. The analysis has indicated that methanol adsorption and surface blocking occur below the onset and the surface is ‘poisoned’ to the highest degree just before the onset, implying that the removal of residues before the onset, if any, is slower compared to the formation. The onset potential is marked by a sudden change in the mechanism as the impedance becomes pseudoinductive. It has also been demonstrated that EIS can be applied for analyzing and singling out different contributions behind electrode performance for methanol oxidation reaction under fuel cell operating condition.