Single pristine poly(p-phenylene vinylene) (PPV) nanofibers were prepared by electrospinning. The fibers were characterized by fluorescence microscopy, scanning electron microscopy, and polarized fluorescence spectra. The results indicated that the fibers were stretched and oriented toward to rollup direction during the electrospinning process and PPV polymer molecules were oriented with their conjugated backbones along the PPV fiber direction. The parallel array of countable PPV nanofibers was assembled into a photoconductor device. The device shows much higher sensitivity to photo detection than device with PPV film, indicating efficient carrier transport in the well-oriented polymer fibers. This facile, easily operated method for the fabrication of well-oriented fibers indicates its potential application in optoelectronic devices. (C) 2012 Elsevier B.V. All rights reserved.