Gold electrodes were modified by silver and gold nanocrystals (NCs) that self-organize onto the surface. Their optical properties were explored by measuring electro-reflectance spectra as a function of electrode potential. Below their oxidation potential, no shift of the reflectance maximum was observed for Ag NCs. This can be explained by a low interfacial capacitance resulting from the impossibility for the electrolyte to penetrate into the hydrophobic layer created by the NCs dodecanethiol ligands. Conversely, a non-monotonous evolution was observed with the electrode potential for oleylamine capped Au NCs.