Photofragmentation with tunable UV radiation has been used to generate a spectrum for the copperbis(benzene) complex, [Cu(C6H6)(2)](2+), in the gas phase. The ions were held in an ion trap where their temperature was reduced to similar to 150 K, whereby the spectrum revealed two broad features at similar to 38200 and similar to 45700 cm1. Detailed calculations using density functional theory (DFT) show the complex can occupy three minimum energy structures with C(2)v and C-2 (staggered and eclipsed) symmetries. Adiabatic time-dependent DFT (TDDFT) has been used to identify electronic transitions in [Cu(benzene)(2)](2+), and the calculations show these to fall into two groups that are in excellent agreement with the experimental data. However, the open-shell electronic configuration of Cu2+ (d(9)) may give rise to excited states with double-excitation character, and the single-excitation adiabatic TDDFT treatment leads to extensive spin contamination. By quantifying the extent of spin contamination and allowing for the inclusion of a small percentage (similar to 10%), the theory can provide quantitative agreement with the experimental data.