The dissociation of carboxylate and divalent calcium ions is investigated at the molecular level in microsolvation experiments by gradually increasing the number of water molecules around the ions. IR photodissociation (IRPD) laser spectroscopy of H2-tagged (Ca2+, AcO-)(H2O)n=8-21 clusters in the ν(CO2-) spectral range combined with RI-B97-D3-BJ-abc/TZVPPD frequency calculations is used to identify the type of ion pairs involved in this process. These results reveal that the ion dissociation follows a multistep mechanism involving in particular pseudobridged monodentate contact ion pairs (CIPs), which are found to be the first intermediate species formed from bidentate CIPs along the ion dissociation path. Altogether, structural assignments suggest a sequence of simple reactions in the first coordination shell of the carboxylate group, leading us to propose two possible dissociation paths. The appearance threshold of monodentate structures is measured at n = 10, with that of solvent-shared ion pairs (SIPs) being potentially at n = 18. By showing in detail how solvation progressively takes over from the ionic interaction in shaping these supramolecular structures, this study can serve as a reference for solving ion-pairing/dissociation problems.