In this paper we present a chemical vapour deposition (CVD) method for the preparation of thin films of poly(1,4-phenylenevinylene) (PPV) on various substrates. The CVD process results in the initial formation of a non-conjugated precursor polymer film, which can be thermally converted into PPV. The films were characterized by various techniques. We also show that these PPV films can be used to fabricate polymer light-emitting diodes (LEDs). A maximum efficiency of 0.002% (photons/electron, external) was achieved.