Organic conducting fiber-like materials hold great promise for the development of nanowires that can act as connections in miniature electronic devices, as an alternative to inorganic nanometer scale structures. This article presents a conducting organic tetrathiafulvalene-based supramolecular material which possesses a rich phase behavior with different packing of the molecules in the different forms, evidenced by electron spin resonance (ESR) spectroscopy. The distinct phases of conducting nanofibers can be easily fabricated through the temperature control of their preparation process from a xerogel by doping with iodine vapors. A total of four conducting phases have been identified conclusively using ESR spectroscopy as the key analytical tool. Three of the phases show a good long-term stability and areas in which the I–V curves have ohmic behavior when studied by current sensing (conducting) AFM. They offer promise for applications where electrical nanometer scale connections are required.