The structural details of [Cu(dMP)(2)](+) (dmp = 2,9-dimethyl-1,10-phenanthroline) at its metal-to-ligand charge-transfer (MLCT) excited-state in acetonitrile were extracted using quantitative analysis of Cu K-edge X-ray adsorption near edge structure (XANES). The study combines two techniques: fitting experimental XANES spectra with a multidimensional interpolation approximation, and calculating theoretical XANES spectra with molecular potentials beyond the muffin-tin approximation. The results of the study show that the best fit of the experimental XANES data must include a solvent molecule binding to the Cu with a short Cu-N distance of 2.00 angstrom. This confirms that the formation of an exciplex is responsible for the excited-state quenching in coordinating solvents, such as acetonitrile. Moreover, the calculations suggest that the formation of this exciplex state is accompanied by significant rocking distortions of the dmp ligands resulting in a 108 degrees angle between the N(solvent)-Cu bond and the C-2 symmetry axis of the dmp ligand. This combined approach allows us to extract molecular configurations that would otherwise be missed in a conventional qualitative XANES analysis.