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 σ 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.