A new strategy to concentrate phospholipids from buttermilk powder was developed using a food-grade green method based on ethanol-modified supercritical carbon dioxide (SC-CO2) extraction. The effects of extraction conditions, namely temperature (50 and 60°C), pressure (30 and 40 MPa), and ethanol concentration (10, 15, and 20%, wt/wt), on the total lipid yield and phospholipid content were investigated. The ethanol concentration had a more significant effect on the total lipid yield and phospholipid content than the temperature and pressure within the ranges studied. The highest phospholipid recovery was achieved at 60°C, 30 MPa, and 15% (wt/wt) ethanol with a total lipid yield of 6.3% (wt/wt), of which 49% (wt/wt) were phospholipids composed of dihydrosphingomyelin (5%), sphingomyelin (24%), phosphatidylethanolamine (22%), phosphatidylserine (2%), phosphatidylinositol (3%), and phosphatidylcholine (44%). The triacylglycerol compositions of extracts obtained by Folch and ethanol-modified SC-CO2 extractions were similar. A sequential pure SC-CO2 and ethanol-modified SC-CO2 extraction was carried out to separate nonpolar lipids in the first fraction, thereby concentrating phospholipids in the second fraction. This sequential extraction produced a highly concentrated phospholipid extract (76%, wt/wt). To the best of our knowledge, this is the highest phospholipid concentration reported from buttermilk powder. Thus, this phospholipid-rich extract can be used in the development of functional foods as a food-grade emulsifier with potential health-promoting effects.