Sufficient amounts of fluorographene sheets with different sheet-size and fluorine/carbon ratio were synthesized for preparing of fluorographene/polyimide hybrids in order to explore the effect of fluorographene on the dielectric properties of hybrid materials. It is found that the fluorine/carbon ratio, width of band gap, and sheet-size of fluorographene play the important roles in determining the final dielectric properties of hybrids. The fluorographene with high fluorine/carbon ratio (F/C ≈ 1) presents broaden band gap, enhanced hydrophobicity, good dispersity and thermal stability, etc. Even at a very low filling, only 1 wt %, its polyimide hybrids exhibited drastically reduced dielectric constants as low as 2.1 without sacrificing thermal stability, improved mechanical properties obviously and decreased water absorption by about 120% to 1.0 wt %. This provides a novel route for improving the dielectric properties of materials and a new thought to carry out the application of fluorographene as an advanced material.