Fluorinated polycarbonate-based UV-curable polyurethane acrylate (F-PCUA) was synthesized by incorporating 1H, 1H, 2H, 2H-Perfluoro-1-octanol to the end of polycarbonate-based PUA chains. The structure of F-PCUA was determined by H-1-NMR, F-19-NMR, and FTIR analyses. The physical, surface, and thermal properties of F-PCUA were also examined. The F-PCUA was used as a hydrophobic additive in PUA coatings, and the water and oil wettability of the UV-cured film was investigated by contact angle measurements. The results showed that the coating system had great hydrophobicity. Furthermore, X-ray photoelectron spectroscopy research confirmed that a hydrophobic fluorine-enriched surface was obtained in the coating system. Moreover, the mechanical and chemical properties of the hydrophobic coatings did not show deterioration with the introduction of elemental F.