Dispersion-corrected density functional theory (DFT-D) calculations, Electron Spin Resonance spectroscopy (EPR), and variable temperature magnetic moment measurements were used to investigate the structure and the electronic/magnetic properties of bispyrazolato-copper(II) coordination polymer and of its hydration product. The Cu(II) ions are antiferromagnetically coupled through the sigma system of the pyrazolate rings in both compounds. Theoretical electron density maps reveal that water molecules interact simultaneously and to a comparable extent with two Cu(II) centers (through the electronegative O end) and two pyrazolate rings (through the partly positively charged H atoms), which is compatible with the observed internuclear distances. DFT-D calculations indicate that low kinetic barriers are involved in the rearrangement of the host structure.