In this work, the electrospinning technique is used to fabricate a polymer-polymer coaxial structure nanofiber from the p-type regioregular polymer poly(3-hexylthiophene-2,5-diyl) (P3HT) and the n-type conjugated ladder polymer poly(benzimidazobenzophenanthroline) (BBL) of orthogonal solvents. Generally, the fabrication of polymeric coaxial nanostructures tends to be troublesome. Using the electrospinning technique, P3HT was successfully used as the core, and the BBL as the shell, thus conceptually forming a p-n junction that is cylindrical in form with diameters in a range from 280 nm to 2.8 µm. The UV-VIS of P3HT/PS blend solution showed no evidence of separation or precipitation, while the combined solutions of P3HT/PS and BBL were heterogeneous. TEM images show a well-formed coaxial structure that is normally not expected due to rapid reaction and solidification when mixed in vials in response to orthogonal solubility. For this reason, extruding it by using electrostatic forces promoted a quick elongation of the polymers while forming a concise interface. Single nanofiber electrical characterization demonstrated the conductivity of the coaxial surface of ~1.4 × 10-4 S/m. Furthermore, electrospinning has proven to be a viable method for the fabrication of pure semiconducting coaxial nanofibers that can lead to the desired fabrication of fiber-based electronic devices.