The authors report on the assembly and photoelectric performance of poly(p-phenylene vinylene) (PPV)/Fe3O4 nanofiber array. The composite nanofibers were fabricated by electrospinning of PPV precursor/Fe3O4 nanoparticle solution, followed by thermal conversion. The Fe3O4 nanoparticles were uniformly dispersed in the PPV matrix. During the electrospinning process, magnetic fields were used to orient the nanofibers. The resulting nanofiber array was assembled directly into a photoconductor device. The photoelectric performances of the devices have been investigated, which show notable light sensitivity, good response speed, wavelength sensitivity, and reproducibility. Electrospinning is thus proposed as a simple and versatile method of fabricating one-dimensional PPV-based photoconductor devices.