New (μ-oxo)bis[trichloroferrate(III)] dianions-based ionic compounds that contain various counterdications were synthesized and characterized with regards to their crystal structures, thermal properties, and magnetic susceptibility. These salts are soluble in polar solvents such as methanol and water. The melting point of these compounds is affected by the dication following the order of triphenylphosphinium > pyridinium > imidazolium dications, and symmetrical dicationicsalts > unsymmetrical ones. In these compounds, the trichloroferrate dianion exists in either a linear or a bent form, which is affected by the dications. Interestingly, the dicationic diferrate compounds show magnetic coupling constants fairly smaller than those reported in literature for diferrate salts in which monocations are the counterion. Furthermore, unlike the diferrate salts associated with separate monocations, the linear diferrate dicationic compounds show magnetic coupling constant lower than that of bent diferrate dicationicsalts.