Molecular weights of {[3,5-(CF3)(2)Pz]Ag}(3), {[3-(C3F7),5-(t-Bu)Pz]Ag}(3), and {[3,5-(i-Pr)(2)Pz]Ag}(3) at various solution concentrations have been investigated using vapor-pressure osmometry. Depending on the concentration, the trinuclear {[3,5-(CF3)(2)Pz]Ag}(3) either dissociates into mono- and dinuclear moieties or remains trinuclear or aggregates to hexanuclear species in toluene. In contrast, {[3-(C3F7),5-(t-Bu)Pz]Ag}(3), which has a bulky and relatively electron-rich pyrazolate, retains the trinuclear form even at low concentrations in toluene. Both {[3,5-(CF3)(2)Pz]Ag}(3) and {[3,5+(i-Pr)(2)Pz]Ag}(3) adopt trinuclear structures in heptane at low concentrations. At higher concentrations, {[3,5-(i-Pr)(2)Pz]Ag)(3) forms hexanuclear species. The aggregation-segregation points are rather sharp and are reminiscent of the all-or-none character of phase transitions. Remarkably, at higher concentrations, the aggregation states of these silver pyrazolates are similar to those expected based on solid-state data.