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This work reports, for the first time, an Ethanolic Two-Phase System (ETPS) based on polypropylene glycol 2000 (PPG 2000), mono-, di-, tri-ethylene glycol, and ethanol. An ionic liquid (IL) (1-butyl-3-methylpyridinium chloride) was used as an adjuvant. This ETPS shows promising results for the extraction of highly hydrophobic compounds. Bixin (model of hydrophobic compounds) migrates completely to the PPG 2000-rich phase, while ascorbic acid (hydrophilic compound) migrated to the opposite phase.