We have recently shown that low surface energy polymeric films can be readily obtained from partially fluorinated hydroxyl-end-capped solventless liquid oligoesters by thermal curing [1]. Photocurable liquid oligoesters can be prepared by further substituting the remaining hydroxyl end groups with acrylic double bonds. A conventional photoinitiator containing 2-hydroxy-2-methylpropiophenone was used to cure the liquid oligoesters. As the fluorine content increases from 0 to about 1.57 wt %, the surface energy decreases by about 14 mN/m. The fluorine level in the outer few nanometers is significantly greater than that in the bulk, as revealed by XPS studies. The driving, force for the surface segregation of fluorinated species comes from the large difference in surface energy between the oligoesters and their fluorinated counterparts.