In the last three decades, greener technologies have been used, aiming at extracting phenolic compounds from vegetable matrices due to the inherent advantages compared to organic solvent-based methodologies. In this work, supercritical CO2 was investigated for recovering phenolic acids from potato peels. Following screening runs for assessing the significant extraction parameters, a Central Composite Design of Experiments was carried out aiming at process optimization, with methanol concentration (MeOH, %) and CO2 flow rate (qCO2, g/min) as independent variables. Both parameters were deemed to impart a significant effect on the final response. Although the major phenolic acid in potato peels is chlorogenic acid (CGA), the main compound extracted was caffeic acid (CFA), present at a concentration of 0.75 mg/g dry peel in the extracts. The optimum extraction conditions were 80 °C, 350 bar, MeOH 20%, and flow rate of 18.0 g/min, which enabled a total phenolic recovery of 37% and a CFA recovery of 82%. The antioxidant activity of the supercritical fluid extraction (SFE) extracts was also measured, with the highest scavenging capacity reaching 73%. The need for using mixtures of water and organic solvents as co-solvents in SFE to enable CGA recovery seems necessary, possibly due to its better dissolution in aqueous solutions than in pure solvents.