In this work, an automated surfactant-assisted dispersive liquid-liquid microextraction approach based on in-a-syringe concept was developed for the first time. The procedure assumed mixing aqueous sample phase and hydrophilic emulsion containing hexanoic acid and sodium hexanoate in a syringe of flow system. Sodium hexanoate acted as an emulsifier in dispersive liquid-liquid microextraction process and it was required for the formation of supramolecular solvent phase. After spontaneous separation of phases in the syringe, the upper supramolecular solvent phase containing target analytes was withdrawn and analyzed. The procedure was applied to the determination of 13 polycyclic aromatic hydrocarbons in tea infusion by high performance liquid chromatography with fluorescence detection. It was shown that the supramolecular solvent provided effective extraction of polycyclic aromatic hydrocarbons and fast phase separation in the syringe without centrifugation. The enrichment factors were in the range of 38–46. The automated microextraction procedure lasted 4 min including syringe cleaning. Under optimal experimental conditions the linear detection ranges were found to be 0.05–50.00 μg L−1 with limits of detection calculated from a blank test, based on 3σ, 0.02–0.04 μg L−1. Recovery values in the range of 85–105% were achieved for tea infusion with a reproducibility expressed as RSD less than 4.1%.