A crystalline product is obtained in high yield when ruthenium(III) chloride is dissolved in dimethylformamide, in the presence of small amounts of hydrochloric acid. The structure of this product has been determined by X-ray diffraction studies. We have found that the obtained product is ionic and may be formulated as (Me2NH2)4Cl(RuCl6), the structure being formed by dimethylammonium cations, chloride anions and hexachlororuthenate(III) anions. The presence of the dimethylammonium cation in this structure suggests that substantial cleavage of DMF has occurred under the relatively mild experimental conditions used in this study. The implications of these findings are briefly discussed.