The compound [(Cu(PPh3)(2))(3)(HATNMe(6))](BF4)(3) has been synthesized and characterized by X-ray crystallography, resonance Raman spectroscopy, and density functional theory (DFT) calculations. The X-ray structure of solvated [(Cu(PPh3)(2))(3)(HATNMe(6))](BF4)(3) [rhombohedral, R (3) over bar, a = b = 21.6404(4) angstrom, c = 53.188(3) angstrom, alpha = beta = 90 degrees, gamma = 120 degrees] shows that the HATNMe(6) ligand is very slightly twisted. The electronic absorption spectrum of the complex in chloroform shows two bands in the visible region attributed to ligand-centered (LC) and metal-to-ligand charge-transfer (MLCT) transitions, respectively. Time-dependent DFT calculations show good agreement with experiment, with two MLCT and one LC transition predicted in the visible region (641, 540, and 500 nm). Resonance Raman spectra of the complex using discrete excitation energies between 647 and 406 nm showed a variation in enhancement patterns consistent with at least two distinct transitions. The absolute Raman cross sections have been evaluated and, through a wavepacket analysis, the amount of distortion along each vibrational mode across the Franck-Condon surface is established from the calculated dimensionless displacement (Delta) values as well as other electronic parameters. The pattern of Delta values shows good agreement with the observed calculated modes, with the MLCT transition, showing much larger Delta values for outer ring modes such as v(93) and v(205) than in the LC transition. This is consistent with the molecular orbitals involved in the two transitions; the donor orbitals for the LC transition have similar outer-ring bonding characteristics compared to the MLCT transition, which has no donor orbital bonding characteristics on the ligand because the donor molecular orbitals are d pi orbitals.