Perfluoroalkyl substituted PolyMethacrylate (PFPM) polymers are today widely used as low surface-energy coatings playing an essential role in microelectronics, anti-fogging, and anti-fouling applications, and even have promising medical applications. It is generally believed that the anti-wetting properties -solely determined by the structures present in the surface region- of these and related polymers arise from the segregation of CF@sub 3@ groups to the surface. However, proof of a direct correlation between surface structure and surface energy, and the importance of order in the underlying bulk, is still lacking as most experimental techniques do not have the required surface sensitivity. For preferentially oriented polymers the asymmetry in chain orientation translates to an asymmetry in the electron charge density as the electron orbitals are oriented along the molecular bonds. Such a charge asymmetry can give rise to a dependence of the Near Edge X-ray Absorption Fine Structure (NEXAFS) on the orientation of the electric field vector of the linearly polarized x-rays relative to the sample. Consequently, such a linear dichroism can be used to study orientation phenomena quantitatively. The required surface sensitivity is obtained by recording simultaneously the more bulk sensitive total (TEY) and the more surface sensitive Auger (AEY) electron yield. Our studies of three PFPM's with different bulk order phases reveal a greater order at the surface than in the bulk, and the surface order parameter is found to correlate with the surface energy. Most importantly, temperature dependent NEXAFS measurements covering several bulk phase transitions show that the achievable surface order, and hence the surface properties, is ultimately limited by the bulk order (phase).