With the development of science and technology, lithium ion batteries have become a representative of modern high-performance batteries due to their excellent performance. In this work, BiNbO4 with the nanowire morphology is fabricated by a simple electrospinning method on a stainless steel mesh cage collector. Here, we demonstrate that the BiNbO4 nanowires display a reversible capacity of 165 mAh g−1 and remarkable cycling stability at a current density of 50 mA g−1. When cycled at 700 mA g−1, BiNbO4 nanowires can maintain the capacity retention of 60% after 700 cycles, revealing better cycling properties than other Bi-based anode materials. In addition, in-situ X-ray diffraction analysis suggests that BiNbO4 nanowires have good electrochemical reversibility. BiNbO4 is transformed into Bi nanocrystallites and Li3NbO4 during the first discharge process. With the continuation of the discharge, active Bi nanocrystallites react with lithium ions to form Li3Bi alloys. This is a reversible process that provides reversible capacity as the reaction proceeds.