Nanostructures always have an advantage in electrochemical research. In this work, the GeNb18O47 nanowires are synthesized by an easy electrospinning method for the first time. We study morphologies and electrochemical properties of as-obtained GeNb18O47 nanowires via the X-ray diffraction, charge/discharge curve, cyclic voltammetry, scanning electron microscopy and transmission electron microscopy. As expected, GeNb18O47 nanowires exhibit impressive charge capacity of 216.9 mAh g−1 at a current density of 100 mA g−1 and high-capacity retention of 93.6% after 200 cycles. Electrochemical analyses show that GeNb18O47 nanowires exhibit the lower redox polarization, smaller charge transfer resistance and higher Li+ diffusion coefficient compared with sol-gel formed bulk sample. Therefore, the GeNb18O47 nanowire is a promising active electrode material for the lithium batteries.