In the present work, we report the preparation of TiO2-carbon/carbon dual nanofibers using an electrospinning technique. The dual nanofibers were synthesized using a modified side-by-side spinneret, which allowed the fabrication of the desired dual nanofiber architecture in a one-step process. A subsequent heat treatment permitted the control on the crystal structure of the synthesized dual nanofibers. Scanning electron microscopy and transmission electron microscopy results confirmed the continuity and duality of the obtained nanofibers. The difference in composition between the fibers composing the dual fibers was clearly observed by energy dispersive X-ray spectroscopy. The effect of heat treatment on crystallinity was evident on the results obtained from the X-ray diffraction and selected area electron diffraction studies; where, depending on the heat treatment conditions, clear signals for anatase and rutile phases of TiO2 were observed. Electrochemical studies suggest an improvement on the conduction properties of TiO2-carbon/carbon dual nanofibers compared to single TiO2-carbon nanofibers, attributed to the carbon nanofiber contribution attached to the TiO2 nanofibers. Based on the morphological and structural features of this novel nanostructured material, and to the electrochemical performance observed, it has a wide range of potential applications.