Diamond-like carbon (DLC) coatings doped with Ag nanoparticles are promising materials for several application, as, for example, a biomaterial. In addition to their numerous properties, when doped with silver, DLCs can acquire antibacterial properties. In this study, Ag/a:C films were deposited by unbalanced magnetron sputtering. The dimension and distribution of silver nanoparticles in the carbon matrix were characterized before and after immersion in different liquid environments, ultra-pure water and NaCl (0.9%). Inductively coupled plasma-optical emission spectroscopy was used to quantify the Ag ions released from the film. Based on the aspect of Ag nanoparticles on the films surface, suggested by atomic force microscopy analysis, scanning electron microscopy was performed to access the dimension and the distribution of the nanoparticles at the surface and, then, to calculate the mass of Ag in the film, before and after exposure to both liquids. Agglomeration and coalescence of the nanoparticles in the film surface were studied and information about the segregation from the bulk to the surface was achieved, also confirmed by X-ray photoelectron spectroscopy analysis.