We investigated reactive fluorinated (meth)acrylate monomers and macromonomers that caused segregation at the cured resin surface of a viscous hydroxy-containing monomer, glycerol 1,3-diglycerolate diacrylate (GDD), and decreased the demolding energy in ultraviolet (UV) nanoimprinting with spin-coated films under a condensable alternative chlorofluorocarbon gas atmosphere. The X-ray photoelectron spectroscopy and contact angle measurements used to determine the surface free energy suggested that a nonvolatile silicone-based methacrylate macromonomer with fluorinated alkyl groups segregated at the GDD-based cured resin surface and decreased the surface free energy, while fluorinated acrylate monomers hardly decreased the surface free energy because of their evaporation during the annealing of the spin-coated films. The average demolding energy of GDD-based cured resins with the macromonomer having fluorinated alkyl groups was smaller than that with the macromonomer having hydrocarbon alkyl groups. The fluorinated alkyl groups were responsible for decreasing the demolding energy rather than the polysiloxane main chains. We demonstrated that the GDD-based UV-curable resin with the fluorinated silicone-based macromonomer was suitable for step-and-repeat UV nanoimprinting with a bare silica mold, in addition to silica molds treated by chemical vapor surface modification with trifluoro-1,1,2,2- tetrahydropropyltrimethoxysilane (FAS3) and tridecafluoro-1,1,2,2- tetrahydrooctyltrimethoxysilane (FAS13).