Tetrathiafulvalene-tetracyanoquinodirnethane charge transfer complex (TTF-TCNQ CTC) represents a promising organic conductive system. However, application of this donor acceptor pair is highly limited, because of its ultrafast crystallization kinetics and very low solubility. In this work, conductive organic nanofibers were generated via, a coelectrospinning process of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-I-IFP) with embedded TTF and TCNQin the shell and core solutions, respectively. Upon supply of the polymer solutions, a core-shell droplet was formed at the exit of the spinneret. The electron donor TTF and the electron acceptor TCNQ migrated toward each other, within the compound droplet, to produce conductive CTC crystals. In the presence of a sufficiently strong electric field, jetting set M at the droplet tip, which yielded solidified PVDF-HFP nanofibers embedded with aligned CTC. Fiber diameters ranged between 100 and 500 nm. X-ray analysis showed strong equatorial reflections (110,200) of oriented copolymer PVDF-HFP crystals (beta-phase) with copolymer,chains oriented along the fiber axis, and of CTC (001), indicating that the CTC molecular planes were aligned parallel to the nanofiber axis. In addition, reflections of unreacted TCNQ(120,220) and TTF (110) crystals were observed. The dectrospun nanofibers were collected to form a fiber mat, which was evaluated as a working electrode in a three electrode cell system, exhibiting differential conductance of 5.23 mu mho.