A series of iron(III)-containing imidazolium salts of the general formula [DRim] [FeX 4 ] (R = 2,6-diisopropylphenyl, IPr, X = Cl, 1; R = IPr, X = Br, 2; R = tertbutyl, t Bu, X = Cl, 3; R = isopropyl, i Pr, X = Cl, 4; R = benzyl, Bn, X = Cl, 5; R = Bn, X = Br, 6) have been prepared in high yields via reactions of anhydrous ferric halides with equivalent of the corresponding N,N-dihydrocarby-limidazolium halides, where 2-6 are novel ones. All of the complexes were characterized by elemental analysis, Raman spectroscopy, electrospray ionization mass spectroscopy, and X-ray crystallography for 1 and 2. All of them were non-hygroscopic and air-stable, with four of them existing as solids (1-4) and two as liquids (5 and 6) at room temperature. A preliminary catalytic study on the coupling of 4-tolylmagnesium bromide with cyclohexyl bromide revealed that 1 and 3 possessed the highest activity. In comparison, 2, 4 and 5 exhibited moderate activity and the least active complex was 6. shown to be capability in this regard. Fe(acac) 3 (acac = acetylacetonate) are also active [10], although the addition of an amine additive was required to achieve a higher yield of the cross-coupled product [11]. Notably, an easily prepared iron(III)-containing imidazolium salt [bmim] [FeCl 4 ] (bmim = 1-butyl-3-methylimidazolium cation) can be used as a recyclable catalyst for the aryl Grignard cross-coupling of alkyl halides [12]. The use of imidazolium chloride can modify the highly hygroscopic FeCl 3 into an non-hygroscopic and air-stable complex, which provides a practical strategy for the design of iron(III)-based catalyst with potential large-scale applications [11].[bmim] [FeCl 4 ] has already been successfully used as a catalyst in other organic transformations, including the Friedel-Crafts sulfonylation of aromatics [13], a Biginelli condensation for the synthesis of dihydropyrimidinones [14], 2,5-norbornadiene dimerization [15], oxidative desulfurization of fuels [16], the glycolysis of poly(ethylene terephthalate) [17], and the regioselective benzylation of arenes and heteroarenes [18].