Studies were conducted to determine the critical micelle concentration (CMC) of phospholipids in vegetable oils and the size of reverse micelles to understand their rejection phenomenon in the membrane process. The CMC values of phosphatidylcholine (PC) in triolein and phospholipids in crude soybean oil were determined to be 440 and 1020 mg/kg, respectively, by using TCNQ (7,7,8,8-tetracyano-quinodimethane) solubilization technique. The surface tension measurements of these samples gave similar values of CMC. From small-angle X-ray scattering (SAXS) analysis, the size of the PC micelles was determined to be in the range of 3.56 to 4.70 nm. The characterization of reverse micelles formed in the oil system was found useful in enhancing the understanding of the possible rejection phenomenon of phospholipids by non-porous polymeric composite membranes used in our earlier studies on vegetable oils and in suggesting suitable types of membranes for the same.