Fluoro-containing polymer with low refractive index was used as the film-forming substance photopolymer holographic material to increase the spatial modulation range of its refractive index. Water soluble, fluoro-containing polymer with low reflective index derived from the copolymers of 2,2,3,3-tetrafluoropropyl methacrylate and methacrylic acid was prepared. The above polymer with low reflective index was used as the film-forming component, together with acrylamide as monomer, methylene blue as light-sensitive dye and triethanol amine as photo-initiator, for the preparation of photopolymer films for holographic recording. The photopolymer with optimized composition exhibited high sensitivity of 19 mJ/cm2 and high diffraction efficiency of 93% at spatial resolution of 1580 lp/mm, better than that with water soluble polyvinyl alcohol (PVA) as the film-forming substance.