We have studied the effect of cholesterol oil curved bilayers using 600 angstrom unilamellar vesicles made of monounsaturated lipids. From small-angle X-ray scattering experiments we were able to detect an asymmetric distribution of lipid densities across certain bilayers. We discovered that, with the exception of diC24 : 1PC bilayers, monounsaturated diacylphosphatidylcholine lipids (diCn : 1PC, n = 14, 16, 18, 20, and 22) form symmetric bilayers. However, the addition of 44 mol % cholesterol resulted in some of these bilayers (i.e., n = 14, 16, and 18) to become asymmetric, where cholesterol was found to distribute unequally between the bilayer's two leaflets. This finding is potentially of relevance to biological membranes made up of different types of lipids and whose local curvature may be dictated by lipid composition.