Tomatoes (Solanum lycopersicum) represent the second most produced and consumed vegetable crop in the world and can be considered a source of various nutrients, such as minerals, fiber, phenolic compounds, and vitamins A (precursors: β-carotene) and E (α -tocopherol). The actions of vitamins in the regulation of biological functions and disease prevention have encouraged the food, cosmetic and pharmaceutical industries to formulate new products. In this sense, extraction procedures integrated with purification protocols should be increasingly considered. This work aims to extract β-carotene and α-tocopherol from tomatoes using ethanol followed by an integrated purification procedure in ethanolic two-phase systems (ETPSs). Initially, phase diagrams for systems based on polypropylene glycol (PPG) + ionic liquids (IL) + ethanol were constructed at 298.15 ± 1.00 K and 0.10 ± 0.01 MPa. The driving force for phase separation is the hydrophilic/hydrophobic balance between the constituents of the system, with the largest biphasic region formed by PPG with a higher molecular weight (PPG 4000), IL formed by short alkyl chain cations, the pyridinium family [C2mpyr]+, and anion [CH3SO3]−. The partitioning of β-carotene and α-tocopherol (pure molecules) was selective with preferential migration of β-carotene to the bottom phase (IL-rich), while α-tocopherol migrated preferentially to the top phase (PPG-rich). In real systems using tomatoes and the best condition of the model system formed by PPG-4000 (18.04 wt%) + [C2mim]Cl (45.56 wt%) and ethanol (36.04 wt%), the partitioning was similar, and the purity was 2.82-fold for β-carotene in the bottom phase and 171.89-fold for α-tocopherol in the top phase.