Electrospinning is a simple technique to prepare polymer fibers in nanometer diameters using very high electrostatic fields. These nanofibers are useful in many applications since the surface area to volume ratio in these fibers is very high. Here we have prepared nanofibers of composites of Polystyrene (PS) with different concentrations (0.05% to 2% w/w) of multi-walled carbon nanotubes (MWCNT) by electrospinning. The fibers are characterized by SEM, TEM, Raman spectra, and TGA. The room temperature electrical conductivity of single fibers of these composites are measured and found to show dramatic improvement in the conductivity due to the addition of MWCNT to the polymer matrix compared to the pure PS.