Electrospray ionization of aqueous solutions of magnesium(II) acetate leads to microhydrated magnesium acetate cations of the type [(CH3COO)(2m-1)Mg-m(H2O)(n)](+) with m = 1-4 and n = 0-4, which are characterized by mass spectrometry and, for the cluster with three water molecules, also by infrared multiphoton dissociation spectroscopy. Density functional theory is used to determine the energies of microhydration for the mononuclear species [(CH3COO)Mg(H2O)(n)](+) with n = 0-6 and the associated changes in molecular structure. While bidentate coordination of the acetato ligand is generally preferred, at higher values of n, a switch to a monodentate coordination becomes energetically competitive.