We study the effect of Cu incorporation on the morphological evolution and the optoelectronic properties of thin Ag films deposited by magnetron sputtering on weakly-interacting SiO2 substrates. In situ and real time spectroscopic ellipsometry data show that by adding up to 4at.% Cu throughout the entire film deposition process, wetting of the substrate by the metal layer is promoted, as evidenced by a decrease of the thickness at which the film becomes continuous from 19.5nm (pure Ag) to 15nm (Ag96Cu4). The in situ data are consistent with ex situ x-ray reflectometry analyses which show that Cu-containing films exhibit a root mean square roughness of 1.3nm compared to the value 1.8nm for pure Ag films, i.e., Cu leads to smoother film surfaces. These morphological changes are coupled with an increase in continuous-layer electrical resistivity from 1.0×10-5Ωcm (Ag) to 1.25×10-5Ωcm (Ag96Cu4). Scanning electron microscopic studies of discontinuous layers reveal that the presence of Cu at the film growth front promotes smooth surfaces (as compared to pure Ag films) by hindering the rate of island coalescence. To further understand the effect of Cu on film growth and electrical properties, in a second set of experiments, we deploy Cu with high temporal precision to target specific film-formation stages. The results show that longer presence of Cu in the vapor flux and the film growth front promote flat morphology. However, both a flat surface and a continuous-layer electrical resistivity that is equal to that of pure Ag films can only be achieved when Cu is deployed during the first 2.4nm of film deposition, during which morphological evolution is, primarily, governed by island coalescence. Our overall results highlight potential pathways for fabricating high-quality multifunctional metal contacts in a wide range of optoelectronic devices based on weakly-interacting oxides and van der Waals materials.