A cationic [Ag-2(bis-NHC)(2)](2+) system behaves as an excellent host for Ag+. In the solid-state variation, Ag...Ag are the only bonding interactions between host and guest, overcoming their inherent electrostatic repulsion. It represents a clear example of ligand-unsupported ("pure") argentophilicity. In solution, we also found evidence for this kind of Ag...Ag approximation, which might be recognized as an initial step of transmetalation mechanisms involving formally closed-shell metal centers as transferring agents.