Incorporation of a solvent vapor-saturated nitrogen purge in an electrospray ionization source is demonstrated as a highly selective method for synthesizing clusters consisting of a transition-metal ion complex and organic solvent molecules for use in studies of the influence of local solvation on structure and reactivity. This new technique first uses collisions to completely remove the residual electrospray solvent from the gas-phase ions and then se-forms clusters by association of solvent molecules from the purge in an expansion as the ions pass through the first and second stages of differential pumping in the electrospray ionization source. The resolvation process is selective in that only clusters with the purge solvent are detected under the optimized conditions reported. Clusters of the tris(2,2’-bipyridyl)iron(II) complex, [Fe(bpy)(3)](2+), with a variety of solvents (acetone, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, ethanol, and methanol) have been prepared by electrospraying a dilute methanolic solution and simply introducing the solvent of interest to the nitrogen purge. Dimethyl sulfoxide and N,N-dimethylformamide are unsuitable as electrospray solvents; nevertheless, clusters with these solvents can be formed using this purge technique. In addition, [Fe(bpy)(3)](2+) has been stabilized in clusters with dimethyl sulfoxide, a solvent which rapidly displaces the bipyridyl ligands of the complex in bulk solution.