Fibers of the ferroelectric poly(vinylidene fluoride-trifluoroethylene) blended with the semiconducting regio-regular poly(3-hexylthiophene) polymer - (PVF2-TrFE/P3HT) were prepared for the first time in air at room temperature using the electrospinning technique that is cheap, fast and reliable. The presence of P3HT assisted in fabrication of PVF2-TrFE fibers at low polymer concentrations in tetrahydrofuran (THF) than currently possible, with the fiber diameters increasing as the concentration of PVF2-TrFE increases. UV/VIS spectroscopy showed that P3HT was uniformly incorporated into the PVF2-TrFE solution with no polymer segregation. Scanning electron microscope images show a reduction in the beading effect and an increase in the quantity of fiber formation when P3HT is incorporated into the solution.