We demonstrate in this communication that large-scale coaxial nanocables of polypyrrole (PPy)/TiO2 can be obtained via three steps: (1) synthesis of TiO2 nanofibers by electrospinning; (2) physical adsorption Fe3+ oxidant on the surface of TiO2 nanofibers; (3) followed by polymerization of pyrrole (from vapor) on the surface of TiO2 nanofibers. During the synthesis, the PPy formed on TiO2 nanofibers as a template and formed PPy/TiO2 coaxial nanocables. TEM image proved that PPy (20 nm thickness) covered the surface of TiO2 nanofibers. Fourier-transform infrared (FTIR), X-ray photoelectron spectra (XPS), and X-ray diffraction patterns (XRD) characterized the chemical structure of the coaxial nanocables. Surface photovoltage spectroscopy (SPS) revealed the surface properties of the PPy/TiO2 coaxial nanocables.