We present a joint theoretical and experimental investigation of small neutral and anionic silver fluoride clusters View the MathML source(AgF)n(-) with n ⩽ 6. We have measured the electron detachment energies of the anions View the MathML source(AgF)n- and determined the adiabatic electron affinities of neutral (AgF)n clusters. Ab initio calculations in the framework of the density functional theory have been performed to investigate the electronic and structural properties of both neutral and anionic species. The localization of the excess electron in the anion is discussed.