In this paper, the formation of liquid crystal structure in preparation of emulsion and the change of those liquid crystal structures during storage and usage were studied. Besides, the rheological and moisturizing property of the liquid crystal structure emulsion was investigated as well. The results show that the liquid crystal structure at oil-water interface in the emulsion forms gradually with cooling process after homogenization. The liquid crystal structure doesn’t change significantly during the storage within 12 months. And after emulsion being stored for 18 months, the crystal structure starts to decompose. Upon application on the skin, the liquid crystal structure of emulsion was found to transform into other form with rubbing, although the liquid crystal structure still remains. The rheological data shows that liquid crystal emulsion exhibits solid-like (elastic) property during storage, which is favorable for good stability. On the other hand, liquid crystal emulsion shows typical shear-thinning property upon usage, which leads to an excellent skin sensory feeling. And the improved moisturizing properties of such emulsion may be attributed to the liquid crystal structure.