The vibrational properties of Na atoms and of Na coadsorbed with CO on Ni(111) have been studied by high-resolution electron energy loss spectroscopy. Loss measurements showed a significant weakening of the alkali–substrate bond as a function of the alkali coverage. Moreover, we found that coadsorbed CO molecules dramatically influence the vibrational properties of Na adatoms. The Na–Ni stretching frequency (22 meV) measured on the Na/Ni(111) system shifted down to 13 meV for the (Na + CO)/Ni(111) surface. This unexpected result was ascribed to a charge transfer from Na to CO. Present findings give new insights on the nature of the alkali–substrate and alkali–CO bond.