A chemical vapor deposition (CVD) technique for the preparation of the conjugated polymer PPV, poly(phenylenevinylene), is presented. The thin films were prepared by CVD of a chlorine precursor poly mer from a dichloro-p-xylene monomer followed by a thermal conversion step. The preparation and apparatus are detailed and results of UV-vis and IR spectroscopy discussed. Spontaneous orientation of the polymer during growth is revealed, which suggests the possibility of fabricating chain-oriented polymers by CVD.