The difference between the transfer of citrate-stabilized Au and Ru nanoparticles from the aqueous phase to toluene was used to develop a simple experimental procedure that can positively identify the formation of bimetallic Au–Ru nanoparticles with the core–shell structure formed in the seed-mediated growth process. The procedure was independently verified by UV–vis spectroscopy, transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX) and X-ray photoelectron spectroscopy (XPS). The experimental results clearly showed that core–shell nanoparticles of Au–Ru were formed by the seed mediated growth method using Au nanoparticle seeds. The reverse order of using Ru nanoparticles as the seeds, on the contrary, could only produce a physical mixture of isolated nanoparticles of Ru and Au under the same experimental conditions.