Poly(p-phenylenevinylene) (PPV) was doped with a perylene dye using the vapor transportation method under vacuum. The used dye was N,N'-bis(2,6-dimethylphenyl)-3,4,9,10-perylenetetracarboxylic diimide (DMP-PTCDI). The concentration of the dye in PPV was estimated by infrared (IR) spectroscopy as a function of doping conditions, such as temperature and time. The concentration was estimated to be typically 1-5 wt%. The dye-doped PPV was used for a photovoltaic device, which was a simple Schottky-type device with an aluminum electrode. The device using dye-doped PPV had a photocurrent response at a wavelength longer than that of a nondoped PPV device, which was caused from the absorption of the dye.