The structures of Dy(CF3SO3)(3) in water, methanol, and 2-propanol have been investigated with the use of multinuclear NMR techniques. Dy(III)-induced O-17 NMR shifts of the solvent afforded estimates of the average number of inner-sphere solvent molecules. Information on the location of the triflate anion was obtained by longitudinal F-19 relaxation rates. The data suggest that the predominant species in the various solvents are [Dy(H2O)(8)][CF3SO3](3), [Dy(CF3SO3)(1 -2)(CH3OH)(6)][CF3SO3], and Dy(CF3SO3)(3)(i-PrOH)(3). Upon addition of water to solutions of Dy(CF3SO3)(3) in anhydrous organic solutions the solvent molecules and the triflate anions are expelled from the first coordination sphere of Dy(III) simultaneously.