Phenolic acids are ubiquitous biomolecules exhibiting a wide range of physiological properties, with application in the pharmaceutical and nutraceutical fields. In this work, aqueous biphasic systems (ABS) formed by polyethylene glycol and sodium polyacrylate, and inorganic salts or ionic liquids as electrolytes, were applied to the purification of caffeic, ferulic and protocatechuic acids, followed by the use of centrifugal partition chromatography (CPC) to reinforce the fractionation process scale-up. In single-step experiments in ABS, high selectivities (SFA/CA = 12.09; SCA/PA = 6.32; SFA/PA = 1.91) and adequate partition coefficients (KCA = 2.78 ± 0.20; KPA = 0.44 ± 0.04; KFA = 0.23 ± 0.01) were achieved using ABS formed by sodium chloride as electrolyte. This system was further applied in CPC, allowing an efficient separation of the three phenolic acids after the optimization of the equipment operational conditions, while demonstrating the potential of polymer-based ABS to be used in liquid-liquid chromatography. Finally, the recovery of the phenolic acids (≥ 65%) with high purity from the ABS phases was demonstrated, followed by the reuse of the phase-forming components.