The hydration structure dynamics of Cu(II) ion is characterized by a combination of classical molecular dynamics simulation and X-ray absorption near-edge spectroscopy. Previous experimental data have been analyzed on the basis of 5- or 6-fold first hydration structure, with a quite well-established equatorial structure. This 4-fold equatorial geometry has been our starting point to develop a simple but effective in silico model, which provides ab initio theoretical X-ray absorption spectra in very good agreement with the experimental data. Our results point out two equally populated 6- and 5-fold hydration structures with remarkable different water residence times of 5 and 98 ps, respectively, and a low free energy barrier between first and second hydration shell.