Seminal papers have highlighted the promoting effect of gold when associated with other metals. There is still a lack of information about the origin of the exceptional electrochemical performances of gold-based nanostructures, known so far as one of the most active electrocatalysts for glucose-based energy conversion devices. In this report, we examined the correlation between the electrocatalytic properties and the surface composition on a line-up of Au-based nanostructures: gold-palladium, gold-platinum binaries, and gold-palladium-platinum ternaries from the so-called Bromide Anion Exchange (BAE) method. BAE enables to obtain carbon supported nanocrystals having high Miller indices. These truncated octahedron nanocrystals present twins as well as (110) facets. Both X-ray photoelectron spectroscopy (XPS) and electrochemical characterizations have shown that the surface of the multimetallic nanomaterials contains less atoms of gold. The most exposed platinum and palladium enable improving glucose electrooxidation reaction kinetics at low electrode potentials. Additionally, XPS measurements have shown that the binding energy (BE) of either Pd or Pt shifts towards low values when associated with Au, indicating strong electronic interactions between the different elements in the multimetallic nanomaterials. These properties have led to improved catalytic performances when tested for CO stripping experiments and glucose (potential fuel) electrooxidation reaction in alkaline medium. (C) 2015 The Electrochemical Society. All rights reserved.