In this work, the direct electropolymerization of poly(para-phenylene)vinylene (PPV) is reported onto silicon and porous silicon substrates. The morphology as well as the chemical properties of electrodeposited PPV are investigated by microscopy techniques (scanning electron microscopy and atomic force microscopy) and Fourier transform IR spectroscopy, respectively. We show that the electrodeposition approach is a viable technique to grow homogeneous PPV thin films without altering the optical properties in terms of photoluminescence. A preliminary study of the electroluminescence properties shows that the Si/PPV/Au device is a potential candidate for the fabrication of a functional hybrid device.