In this manuscript, we prepared gold nanorods (Au-NRs) through "silver-assisted seeded methodology" and studied their outermost layer using XPS spectroscopy and ab initio calculations to compare the chemical states of the constituents of the metallic core. Supporting first-principles calculations employing a relativistic, full-potential and all-electron method, with augmented plane waves plus local orbitals as a basis set, ensure proper treatment of the core electron states. Three significant findings can be reported. First, we found that besides Au (0), there are two chemical states for silver, namely Ag (0) and Ag(I), on the Au surface. Our results corroborate with recent results reported in the literature, indicating that Ag monolayer can be oxidized to Ag(I) during the steps of centrifugation and washing with diluted CTAB solution. Second, ab initio simulations showed that Ag atoms have different binding energies, depending on their configuration in Au-NRs (whether silver atoms are found on the surface or if they are spread in bulk as interstitial or substitutional defects). Third, theoretical studies showed that silver atoms located at interstitial sites could distort the crystalline structure, and, therefore, we do not expect interstitial Ag to occur in Au-NRs.