Native or modified lecithins are widely used as a multifunctional ingredient in the food industry. A fractionation process of sunflower lecithin (a non GMO product) with absolute ethanol was used for obtaining enriched fractions in certain phospholipids under different experimental conditions (temperature 35-65 A degrees C, time of fractionation 30-90 min, ethanol/lecithin ratio 2:1, 3:1). Phospholipid enrichment in PC and PI fractions was obtained and analyzed by P-31 NMR determinations. The percent extraction coefficients for different phospholipids (%E-PC, %E-PE and %E-PI) in both fractions were calculated. Values of %E-PC in PC fractions significantly increased (p < 0.05) from 12.8 (35 A degrees C, 30 min, 2:1) to 57.7 (65 A degrees C, 90 min, 3:1) at increasing temperature and incubation time. %E-PE varied from 3.0 to 18.3 in the same fraction while %E-PI presented lower values (< 3%) under all the conditions assayed. The study of the effect of the operating conditions on the fractionation process evidenced a relevant influence of temperature, incubation time and to a minor extent of the ethanol/lecithin ratio on the enriched fraction yield% and selectivity of the main phospholipids (PC, PI, PE) estimated by %E-PL. Response surface methodology (RSM) was utilized to explain the influence of the different parameters to optimize this process.