A series of comb like fluorinated poly(oxyethylene)s having different content of fluoroalkyl side group were prepared to examine the effect of the surface structure variation on the surface properties When the thin films of the polymers having >= 58 mol% of fluoroalkyl side groups were annealed, surface energy decreased and surface stability against polar liquids improved This surface property behavior was found to be very well correlated with changes of the paracrystalline structure orientation and scattering unit numbers after the annealing process However the average tilt angle and d spacing of the fluoroalkyl side group and the paracrystalline ordering of the thin films did not change if any after the annealing process Near edge X-ray absorption fine structure (NEXAFS) spectroscopy and grazing incidence X ray diffraction (GIXD) were used to determine the surface structure, and contact angle measurements were conducted to measure the surface properties