The gas-phase Ag+(CH3OH)(n) ions are studied by infrared photodissociation spectroscopy in the OH-stretch region. An analysis of the spectra with the aid of density functional theory calculations suggests that a coordination number of three is favored in the cases of Ag+(CH3OH)(2)center dot N-2, Ag+(CH3OH)(3), Ag+(CH3OH)(5), and probably of Ag+(CH3OH)(4). For the first two complexes, two-coordinated structures are also identified as minor isomers, which are indicative of the 5s-4d hybridization in Ag+. The coordination geometries of Ag+(CH3OH)(n) are similar to those of Ag+(H2O)(n), but different from tetrahedral coordinations of Ag(I) commonly found in neat solvents. (C) 2010 Elsevier B.V. All rights reserved.