A liquid oxygen-compatible epoxy resin of fluorinated glycidyl amine (TFEPA) with a low viscosity of 260 mPa·s in a wide range of temperatures, from room temperature to 150 °C, was synthesized and used to decrease the viscosity of phosphorus-containing bisphenol F epoxy resins. And the forming process and application performances of this resin system and its composite were investigated. The viscosity of the bisphenol F resin was decreased from 4925 to 749 mPa·s at 45 °C by mixing with 10 wt.% TFEPA, which was enough for the filament winding process. Moreover, the processing temperature and time windows were increased by 73% and 186%, respectively. After crosslinking, the liquid oxygen compatibility was preserved, and its tensile strength, elastic modulus, and breaking elongation at −196 °C were 133.31 MPa, 6.59 GPa, and 2.36%, respectively, which were similar to those without TFEPA. And the flexural strength and modulus were 276.14 MPa and 7.29 GPa, respectively, increasing by 21.73% in strain energy at flexural breaking, indicating an enhanced toughness derived from TFEPA. Based on this resin system, the flexural strength and toughness of its composite at −196 °C were 862.73 MPa and 6.88 MJ/m3, respectively, increasing by 4.46% and 10.79%, respectively.