A series of fluorine-silicon block urethane acrylates (PSi-FMPG-IPDI-HEMA) were synthesized from hydroxypropyl-terminated polysiloxane (PSi), newly-prepared fluorodiol (FMPG), isophorone diisocyanate (IPDI) and hydroxyethyl methacrylate (HEMA). Their molecular structures were characterized by Fourier transform infrared and gel permeation chromatography. The compatibility of the oligomers with HFMA was validated using UV–vis transmittance analysis. The thermal stability, water and chemical resistance, contact angles and anti-adhesive performance of the films were measured. It was found all the films had good thermal properties, and excellent water and chemical resistance. The FMPG content affected the surface energy and anti-adhesive performance of the films. The films with more FMPG presented lower surface energy, lower peel strength, and higher residual adhesion. More importantly, the release films designed based on the fluorine-silicon block urethane acrylates had tremendous application potential.