At 100 K, the title molecular salt, C3H8NO+·C2F6NO4S2−, has orthorhombic (P212121) symmetry; the amino H atom of bis(trifluoromethanesulfonyl)amine (HNTf2) was transferred to the basic O atom of dimethylformamide (DMF) when the ionic liquid components were mixed. The structure displays an O—H...N hydrogen bond, which links the cation to the anion, which is reinforced by a non-conventional C—H...O interaction, generating an R22(7) loop. A further very weak C—H...O interaction generates an [001] chain.