A series of ionic iron(III) complexes of general formula [HLn][FeX4] (HL1 = 1,3‐dibenzylbenzimidazolium cation, X = Cl, 1; HL1, X = Br, 2; HL2 = 1,3‐dibutylbenzimidazolium cation, X = Br, 3; HL3 = 1,3‐bis(diphenylmethyl)benzimidazolium cation, X = Br, 4) were easily prepared in high yields by the direct reaction of FeX3 with 1 equiv. of [HLn]X under mild conditions. All of them were characterized using elemental analysis, Raman spectroscopy and electrospray ionization mass spectrometry, and X‐ray crystallography for 1 and 4. In the presence of magnesium turnings and LiCl, these air‐ and moisture‐insensitive complexes showed high catalytic activities in direct cross‐couplings of aryl phosphates with primary and secondary alkyl bromides with broad substrate scope, wherein complex 4 was the most effective.