Metal-ion-containing ionic liquids (ILs) represent a promising subclass of ILs since they may have interesting magnetic, luminescence or catalytic properties. Apart from a few examples of ILs based on rare earth metal ions, most investigations on metal-based ILs have been limited to transition metals (MZ+) or Al3+ in [MXn](n-z)− anions containing compounds (where X = halide−, SCN−, Tf2N−, (OC(CF3)3)−, (F6-acac)−) or as inorganic ILs with POM anions [MTiW11O39]5-/6-. The examples of ILs containing transition metal-based cations are limited to derivatives of N-alkylimidazoles, R1-NH-R2 or metallocenium-based ligands. Herein we discuss about the synthesis, structural characterization and catalytic properties of a new class of ILs which contain septuply positively charged antiferromagnetically coupled {FeIII3O(RCOO)6L3}7+ cationic triangles [1]. A survey of the Cambridge Crystallographic Database (CSD) up to Dec. 2012 reveals that more than 1100 crystal structures of metal carboxylates containing μ3-oxo bridged metal triangle motifs have been deposited. However, so far the use of this motif in ILs is unprecedented.formula