An effective and simple surfactant-mediated microextraction of synthetic dyes from solid-phase food samples into the primary amine-based supramolecular solvents is presented for the first time. The developed procedure involved two stages: (i) an isolation of dyes from a solid-phase food sample into a micellar solution of the primary amine; (ii) a preconcentration of the extracted dyes into the supramolecular solvent phase generated from the obtained micellar solution under a coacervation process. The microextraction procedure was applied for the determination of synthetic dyes in confectionery, dried fruits, and spices samples. The supramolecular solvent formed from aqueous micelle aggregates of 1-octylamine due to coacervation induced by thymol provided maximum extraction recovery values for synthetic dyes. In the proposed two-stage extraction procedure the micellar solution of primary amine was a media for analytes isolation from solid-phase and their followed preconcentration.