We propose new strategy to facilitate the fabrication of conjugated polymer fiber with higher oriented structures, which focused on electrospinning of a blend solution of regioregular poly(3-hexylthiophene) (rr-P3HT) and poly(vinyl pyrrolidone) (PVP). SEM observation revealed that the blend system forms homogeneous composite nanofibers. This system exhibits the specific feature of strong interchain contribution of P3HT from UV-vis absorption, fluorescence spectroscopic, XRD, and photoelectron spectrometic (for HOMO levels) investigations. We also demonstrate the removal of the PVP component from the P3HT/PVP composite fibers through the selective extraction and such strong interchain stacking of pristine P3HT fiber mat can be remarkably maintained.