Fluorine-doped graphene sheets (F-doped GSs) were synthesized by arc discharge. The products were characterized by scanning and transmission electron microcopies, X-ray diffraction, Raman and X-ray photoelectron spectroscopies. The F-doped GSs contain about 10 wt% F. They are mainly multi-layered, with a much larger size than pure GSs, and are super-hydrophobic.