A hybrid film of graphene decorated with poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) nanoparticles is fabricated by a simple non-solvent induced precipitation method. The structure of the graphene film and graphene/MEH-PPV hybrid film are investigated by scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectroscopy. The large specific surface area of graphene sheets makes it an ideal support for depositing MEH-PPV nanoparticles as well as preventing aggregation of the nanoparticles. The graphene/MEH-PPV hybrid film is superhydrophobic, which is attributed to the increase in surface roughness as a result of random decoration of MEH-PPV nanoparticles on the graphene sheets. The MEH-PPV nanoparticles endow the graphene hybrid film with strong photoluminescence. The hybrid film also shows excellent conductivity and high thermal stability. The graphene/MEH-PPV hybrid film thus prepared may find potential applications in various devices where integrated properties of superhydrophobicity, conductivity and luminescence are required.