Efficient separation and preconcentration of inorganic Sb species in different water samples were performed in this work by a novel dispersive liquid–liquid microextraction (DLLME) method based on the application of a magnetic ionic liquid (MIL) and electrothermal atomic absorption spectroscopy (ETAAS) detection. The Sb(III) species was selectively extracted by complexation with ammonium diethyldithiophosphate (DDTP) and 45 μL of the MIL trihexyl(tetradecyl)phosphonium tetrachloroferrate ([P_6,6,6,14]FeCl₄) as extractant. Subsequently, a magnetic rod was applied for phase separation, introducing it directly into the sample solution, and the MIL phase was then diluted in chloroform. Afterwards, 15 μL of this solution was injected into the graphite furnace of ETAAS for Sb determination. A multivariate study was performed to obtain the optimal extraction conditions. Selective reduction of Sb(V) to Sb(III) with 1% (w/v) KI before preconcentration was applied for total inorganic Sb determination and Sb(V) concentration was calculated by subtraction. The analytical performance of the method included extraction efficiencies of 98.0% for Sb(III) and 92.6% for Sb(V), LOD of 0.02 μg L⁻¹ for Sb(III) and relative standard deviations of 3.1% for Sb(III) and 3.5% for Sb(V) (at 6 μg L⁻¹ Sb(III) and Sb(V), n = 10). The calibration linear range was 0.08–20 μg L⁻¹. The results showed that the proposed methodology was highly sensitive and selective for Sb speciation analysis in tap, dam, mineral, wetland, underground, rain and river water samples.