In this work, a new supramolecular solvent (SUPRAS) was prepared for the first time using hexafluorobutanol (HFB) and farnesol (FO). FO acts as an amphiphile and HFB as a coacervation inducer and density regulator. The method of dispersive liquid‐liquid microextraction followed by high‐performance liquid chromatography, supported by a vortex technique, was established using the prepared SUPRAS for the determination of Sudan dyes in aqueous samples. The extraction parameters, including FO content, HFB content, vortex time, salt addition, and solution pH, were thoroughly investigated and optimized. Under the optimized conditions, the linearity range is 10–750 ng/mL for Sudan I, and 10–1000 ng/mL for Sudan III and Sudan IV, respectively. The limits of detection for Sudan dyes were in the range of 0.8–3.1 ng/mL. The inter‐ and intra‐day relative standard deviations for Sudan dyes were in the range of 1.3%–4.1% and 0.2%–2.6%, respectively. Finally, the proposed method was applied to the determination of Sudan dyes in beverage and river water samples with recoveries ranging from 93.9% to 122.1%. Compared to conventional techniques for the extraction of Sudan dyes in real samples, the proposed method is simpler, faster, and more environmentally friendly.