The molecular structure and dynamics of the photoexcited metal-to-ligand-charge-transfer (MLCT) state of [Cu-I(dmP)(2)](+), where dmp is 2,9-dimethyl-1,10-phenanthroline, in acetonitrile have been investigated by time-domain pump-probe X-ray absorption spectroscopy, femtosecond optical transient spectroscopy, and density functional theory (DFT). The time resolution for the excited state structural determination was 100 ps, provided by single X-ray pulses from a third generation synchrotron source. The Cooper ion in the thermally equilibrated MLCT state has the same oxidation state as the corresponding copper(II) complex in the ground state and was found to be penta-coordinate with an average nearest neighbor Cu-N distance 0.04 Angstrom shorter than that of the ground state [Cu-I(dMP)(2)](+). The results confirm the previously proposed "exciplex" structure of the MLCT state in Lewis basic solvents. The evolution from the photoexcited Franck-Condon MLCT state to the thermally equilibrated MLCT state was followed by femtosecond optical transient spectroscopy, revealing three time constants of 500-700 fs, 10-20 ps, and 1.6-1.7 ns, likely related to the kinetics for the formation of the triplet MLCT state, structural relaxation, and the MLCT excited-state decay to the ground state, respectively. DFT calculations are used to interpret the spectral shift on structural relaxation and to predict the geometries of the ground state, the tetracoordinate excited state, and the exciplex. The DFT calculations also indicate that the amount of charge transferred from copper to the dmp ligand upon photoexcitation is similar to the charge difference at the copper center between the groundstate copper(I) and copper(II) complexes.