AbstractSummary: 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.TEM image of individual PPy/TiO2 coaxial nanocable.magnified imageTEM image of individual PPy/TiO2 coaxial nanocable.