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The reaction of dimethylamine hydrochloride, 18-crown-6 and ferric chloride in ethanol yields the title compound, (C2H8N)[FeCl4]·C12H24O6, which exhibits an unusual supramolecular structure. The protonated dimethylamine contains one NH2+ group, resulting in a 1:1 supramolecular rotator–stator structure (CH3—NH2+—CH3)(18-crown-6), through N—H...O hydrogen-bonding interactions between the ammonium group of the cation and the O atoms of the crown ether. In the crystal, all three components lie on a common crystallographic mirror plane normal to [010].