Introducing metallic nanoparticles, such as Au, on a substrate as a surfactant or wetting inducer has been demonstrated as a simple but effective way to facilitate the formation of ultra-thin silver layers (UTSLs) during the subsequent Ag deposition. However, most studies have paid much attention to the applications of UTSLs assisted by metallic surfactants but neglected the underlying mechanisms of how the metallic surfactant affects the formation of UTSL. Herein, we have applied in situ grazing-incidence wide-/small-angle X-ray scattering to reveal the effects of the Au surfactant or seed layer (pre-deposited Au nanoparticles) on the formation of UTSL by high-power impulse magnetron sputter deposition (HiPIMS) on a zinc oxide (ZnO) thin film. The comprehensive and in-depth analysis of the in situ X-ray scattering data revealed that the pre-deposited Au nanoparticles can act as additional defects or growth cores for the sputtered Ag atoms despite using HiPIMS, which itself forms many nucleation sites. As a result, the formation of a continuous and smooth UTSL is reached earlier in HiPIMS compared with bare ZnO thin films. Based on the mechanism revealed by the in situ measurements, we provide insight into the formation of UTSL and further UTSL-based applications.