Rare-earth metal sesquioxides (RE₂O₃) are stable compounds that require high activation energies in solid-state reactions or strong acids for dissolution in aqueous media. Alternatively, dissolution and downstream chemistry of RE₂O₃ have been achieved with ionic liquids (ILs), but typically with additional water. In contrast, the anhydrous IL 1-butyl-3-methylimidazolium acetate [BMIm][OAc] dissolves RE₂O₃ for RE = La–Ho and forms homoleptic dinuclear metal complexes that crystallize as [BMIm]₂[RE₂(OAc)₈] salts. Chloride ions promote the dissolution without being included in the compounds. Since the lattice energy of RE₂O₃ increases with decreasing size of the RE³⁺ cation, Ho₂O₃ dissolves very slowly, while the sesquioxides with even smaller cations appear to be inert under the applied conditions. The Sm and Eu complex salts show blue and red photoluminescence and Van Vleck paramagnetism. The proton source for the dissolution is the imidazolium cation. Abstraction of the acidic proton at the C²-atom yields an N-heterocyclic carbene (imidazole-2-ylidene). The IL can be regenerated by subsequent reaction with acetic acid. In the overall process, RE₂O₃ is dissolved by anhydrous acetic acid, a reaction that does not proceed directly.