Black beans (P. vulgaris) are highly consumed after different processing treatments, which generate by-products with high potential as functional ingredients with nutraceutical properties. This study assesses the supercritical CO2 extraction (SC-CO2) as selective, and green alternative to obtain non-polar phytochemicals from a black bean by-product. A Box-Behnken design was conducted to evaluate pressure (100-400 bars), temperature (40-70°C), and 70% aqueous ethanol as co-solvent with flow rate (1-3 g/min) on total extraction yield, fatty acid (FA) composition, and phytochemical profile through GC-MS. Co-solvent and pressure-temperature interaction were found to significantly influence the yield. The maximum yield was 2.03 mg/g at 100 bar, 40°C and 2 g/min, like hexane extraction. Higher alkanes were mainly extracted with hexane while SC-CO2 selectively extracted compounds with potential biological activities. Solubility in CO2 of these phytochemicals, saturated and monounsaturated FAs showed a positive effect with temperature increase. This combination of findings provides insight into the effect of temperature and co-solvent on non-polar phytochemicals extraction. All rights reserved, Elsevier.