The guanidine-quinoline ligand dimethylethylene-guanidinoquinoline (DMEGqu) is able to stabilise bis(chelate)copper complexes in an intermediate geometry between tetrahedral and square-planar environments. The structures of the obtained complexes model the entatic state and have been investigated in solid state by single-crystal X-ray diffraction and in the solid state and in solution by X-ray absorption spectroscopy. The dimethylethyleneguanidine (DMEG) unit of the DMEGqu ligand displays a smaller steric encumbrance than the tetramethylguanidine (TMG) counterpart; this allows slightly larger structural changes upon oxidation than those for the TMG counterparts. Moreover, triflate coordination was possible for the Cu-II DMEG complexes. DFT analyses revealed that good structural and optical descriptions are possible through the use of the hybrid functionals B3LYP and TPSSh in combination with the triple-zeta basis set def2-TZVP and the inclusion of empirical dispersion with Becke-Johnson damping and a suitable solvent model. The orbital analysis gives insights into the electronic structure of the complexes and their charge-transfer behaviour.