The use of gaseous species has been proposed in the literature to counteract the three-dimensional growth tendency of noble metals on dielectric substrates and favor an earlier percolation without compromising electrical properties. This “surfactant” effect is rationalized herein in the case of O2 presence during magnetron sputtering deposition of Ag films on SiO2. In situ and real-time techniques (X-ray photoemission, film resistivity, UV–visible optical spectroscopy) and ex situ characterizations (X-ray diffraction and transmission electron microscopy) were combined to scrutinize the impact of O2 addition in the gas flow (%O2), revealing three regimes of evolution of film resistivity, morphology, structure, and chemical composition. At low oxygen flow conditions (%O2 < 4), the observed drastic decrease of the percolation threshold is assigned to a combination of (i) a change in nanoparticle density, wetting, and crystallographic texture and (ii) a delayed coalescence effect. The driving force is ascribed to the presence of specific adsorbed oxygen moieties, the nature of which starts evolving at intermediate oxygen flow conditions (10 ≤ %O2 < 20). At high oxygen flow (20 ≤ %O2 < 40), the found detrimental impact on film resistivity is assigned to an actual oxidation in the form of a Ag2O-like poorly crystallized compound. For all %O2, a composition gradient is observed across the film thickness, with a more metallic Ag at the substrate interface. A correlation between percolation and the nature of the detected O moieties is observed. In parallel to an oxygen spillover mechanism, this gradient can be explained by the competition between different surface processes occurring before percolation, namely, aggregation, metal oxidation, and substrate reactivity. Such findings pave the way to a rational use of O2 as a modifier for Ag growth.