The lamellar liquid crystalline phase in the system consisting of sodium oleate (NaOL), oleic acid (OLA), and water was determined. The interlayer spacing (d) of the lamellar liquid crystal was measured through small angle X-ray diffraction, which indicated that oleic acid molecules were solubilized between the end methyl groups at low concentrations, and then were located within the hydrocarbon chain layer with further increase of its concentration. Cross-linking agents were added to the system, which were found being located partly in between the end methyl groups and partly within the hydrocarbon chain layers. The liquid crystal phase of NaOL/OLA/H2O system with the cross-linking agent was polymerized at 60 °C, which turned out to be a mixture of liquid crystals and solids. Interlayer spacing decreased by about 10 Å, indicating a disruption of the ordered structure by the polymerization. The polymerization took place not only within the hydrocarbon layer, but also in between the layers separated by the end methyl groups. The resulting polymer lowered the surface tension of water to below 30 mN/m, with a critical micellization concentration of about O.25g/L.