Experimental redox potentials of the couples [Cu(R-L-n)(CH3CN)](2+,+), where L-1 is bis-(pyridine-2-ylmethyl)-benzylamine, L-2 is (pyridine-2-ylethyl)(pyridine-2-ylmethyl)-benzylamine, and R is H, Me, or CF3, were determined in dichloromethane solution. The compounds exhibited one simple quasi-reversible wave over the measured potential range of -500 to +1200 mV, and the E-1/2 values varied from +200 to +850 mV versus SCE. These experimental values were correlated with redox potentials calculated using density functional theory. The optimized geometries and the predicted redox potentials were obtained using the BP86 functional and a combination of the basis sets LACV3P** (for Cu) and cc-pVTZ(-f) (for light atoms). A distortion analysis of all of the optimized geometries for both oxidation states was performed using the generalized interconversion coordinate (p. A linear relation was obtained between this parameter and the redox potentials. However, the [Cu(CF3-L-1)(CH3CN)]+ complex showed the largest deviation, which was explained by the more-rigid structure of the ligand.