Thermal behavior, molecular aggregation structure, and water repellency for poly{2-[(perfluorooctylethyl)carbamate]ethyl} acrylate (PFAUr-C-8) were studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), wideangle X-ray diffraction (WAXD), grazing-incidence wide-angle X-ray diffraction (GI-WAXD), contact angle measurements, and X-ray photoelectron spectroscopy (XPS). The impact of the carbamate linker was verified by comparison with poly[2(perfluorooctyl)ethyl] acrylate (PFA-C-8). PFAUr-C-8 exhibited two phase transitions at 357 K and 416 K, whereas PFA-C-8 showed a single-phase transition at 347 K. Both PFAUr-C-8 and PFA-C-8 formed a bilayered hexatic smectic-B phase at room temperature. Although the lamellar structure for the fluoroalkyl (R-f) groups was immediately lost in PFA-C-8 after disordering of the lateral translational order, PFAUr-C-8 maintained a stacked lamellar structure without lateral translational order. PFAUr-C-8 exhibited excellent water repellency at room temperature similar to PFA-C-8 . The outstanding thermal stability of the lamellar structure in PFAUr-C-8 is attributed to the cohesive interaction of the carbamate linkage.