A ligand (L1) (bis(aminoethyl)[2-(4-quinolylmethyl)aminoethyl]amine) containing a 4-quinolylmethyl group attached to one of the terminal amino groups of tris(2-aminoethyl)amine (tren) has been prepared, and its protonation constants and stability constants for the formation of Cull complexes have been determined. Kinetic studies on the formation of Cu2+ complexes in slightly acidic solutions and on the acid-promoted complex decomposition strongly suggest that the Cu2+-L1 complex exists in solution as a mixture of two species, one of them showing a trigonal bipyramidal (tbp) coordination environment with an absorption maximum at 890 nm in the electronic spectrum, and the other one being square pyramidal (sp) with a maximum at 660 nm. In acidic solution only a species with tbp geometry is formed, whereas in neutral and basic solutions a mixture of species with tbp and sp geometries is formed. The results of density functional theory (DFT) calculations indicate that these results can be rationalized by invoking the existence of an equilibrium of hydrolysis of the Cu-N bond with the amino group supporting the quinoline ring so that CuL1(2+) would be actually a mixture of tbp [CuL1(H2O)](2+) and sp [CuL1(H2O)(2)](2+). As there are many Cu2+-polyamine complexes with electronic spectra that show two overlapping bands at wavelengths close to those observed for the Cu2+-L1 complex, the existence of this kind of equilibrium between species with two different geometries can be quite common in the chemistry of these compounds. A correlation found between the position of the absorption maximum and the T parameter measuring the distortion from the idealized tbp and sp geometries can be used to estimate the actual geometry in solution of this kind of complex.