Polymer fibers were prepared by an electrospinning method utilizing a copper wire electrode in a capillary tube. The morphology of electrospun poly(vinyl alcohol) (PVA) fibers was observed, and was found to be dependent on the wire electrode tip position in the capillary tube, the concentration of the polymer solution, the distance between the electrodes, and the applied voltage. By using the wire electrode, the experimental setup is simple and the distance between the electrodes and the applied voltage can be easily reduced. Furthermore, the preparation of poly(3-hexylthiophene) (P3HT) fibers was carried out. P3HT fibers were successfully prepared by mixing poly(ethylene oxide) (PEO) in P3HT solution. Orientation control was also carried out by depositing the fibers on a rotating collector electrode, and the alignment of the P3HT: PEO fibers was confirmed. Anisotropy of the optical absorption spectra was also observed for the aligned fibers. (C) 2010 The Japan Society of Applied Physics