The damping processes of electronic collective excitations of Ag/Ni(1 1 1) were studied by high-resolution electron energy spectroscopy. The FMHM of the Ag surface plasmon was reported as a function of Ag thickness, primary electron beam energy, Ag surface plasmon energy, and parallel momentum transfer. The broadening of the Ag surface plasmon was found to be related to 5sp–5sp transitions, for which a critical wave vector of 0.2 Å−1 exists. Moreover, we provide a direct evidence of the occurrence of chemical interface damping in thin films, upon doping the Ag/Ni(1 1 1) system with K adatoms. The enhanced plasmon broadening in K/Ag/Ni(1 1 1) was ascribed to the existence of additional electron–hole decay channels at the K/Ag interface.