P3HT-PEO blend nanofibers were produced by electrospinning from chloroform solutions. A morphological study was carried out as a function of the processing parameters as well as the ratio between the two polymers. The fibers containing at least 60wt.% of P3HT presented striated surfaces that could be explained by the alignment of the polymer domains along the fiber axis. The structural arrangement of the polymers was found to vary according to the polymers relative contents. The maximum electrical conductivity found for unaligned mats was 0.16 S/cm and increased to 0.3 S/cm when the nanofibers were aligned along a preferential direction. Crown Copyright (C) 2008 Published by Elsevier B.V. All rights reserved.