Electrospinning is a simple method of obtaining polymer fibers with nanometer diameter. The increase in the ratio of surface area to volume in the case of such fibers, make them attractive in applications such as sensors, etc. It is difficult to electrospin Polypyrrole (PPy) directly to form fibers. Hence electrospinning is attempted with a composite formed with PPy and any other insulating polymer such as Polyethylene oxide (PEO), Polystyrene (PS), etc. The concentration of PPy can be varied to improve the electrical or sensing properties of the resulting composite. In the present report, the PEO-PPy composite fibers with different weight percentages (10% to 50% w/w) are prepared by electrospinning process. The fibers obtained are characterized using SEM (Scanning Electron Microscope) and TEM (Transmission Electron Microscopy). I-V Characteristics are studied for single and multiple aligned fibers obtained on gold electrodes. The variation of electrical conductivity with different concentration of PPy is discussed. © 2006 Materials Research Society.