The local environment of the Cu2+ ion in copper chloride solutions has been investigated by x-ray absorption spectroscopy. Three aqueous solutions of CuCl2 with increasing Cl-/Cu2+ ratio have been examined, An advanced data analysis including multiple-scattering effects produced quantitative information on the chlorocuprate complexes present in solution and provided evidence for an increasing degree of complex formation between Cu2+ and Cl- ions with increasing chloride concentration. The presence of Cu-CI interactions at the axial site has been detected in a 0.1 M CuCl2 solution for the first time. At higher chloride concentrations (Cl-/Cu2+ ratios equal 10 and 30) the equatorial positions in the distorted octahedral copper coordination are occupied by 3.2 and 3.0 oxygens and 0.8 and 1.0 chloride ions, respectively, while the axial positions are occupied by 1.2 and 1.0 oxygens and 0.8 and 1.0 chloride ions, respectively. The results are found to be consistent with previous x-ray and neutron diffraction studies and with experimental data on the complex formation. (C) 1997 American Institute of Physics.