Visible light excitation of [Cu-I(dmp)(2)](BArF), where dmp is 2,9-dimethyl-1,10-phenanthroline and BArF is tetrakis(3,5-bis(trifluoromethylphenyl))borate, in toluene produces a photoluminescent, metal-to-ligand charge-transfer (MLCT) excited state with a lifetime of 98 +/- 5 ns. Probing this state within 14 ns after photoexcitation with pulsed X-rays establishes that a Cu-II center, borne in a Cu-I geometry, binds an additional ligand to form a five-coordinate complex with increased bond lengths and a coordination geometry of distorted trigonal bipyramid. The average Cu-N bond length increases in the excited state by 0.07 Angstrom. The transiently formed five-coordinate MLCT state is photoluminescent under the condition studied, indicating that the absorptive and emissive states have distinct geometries, The data represent the first X-ray characterization of a molecular excited state in fluid solution on a nanosecond time scale.