With niobium oxalate as the niobium source and hollow carbon sphere as a template, a synthesis can be achieved of hollow C/Nb2O5 microspheres with unique morphology by adopting a simple hydrothermal method, followed by an investigation made of the microstructure of as-prepared C/Nb2O5 microspheres by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results show that the hollow carbon spheres with a diameter of about 1 μm are coated with Nb2O5, and the hollow C/Nb2O5 microspheres are characterized with a unique“hydrangea”shape leading to a significant increase of the specific surface area. The initial discharge specific capacity of the C/Nb2O5 microspheres and Nb2O5 microspheres at a current density of 40 mA/g is 402.26 mA·h/g and 336.44 mA·h/g, respectively. After 50 cycles, the discharge capacity of the C/Nb2O5 microspheres is maintained at 192.38 mA·h/g, with the discharge capacity of Nb2O5 microspheres being only 4.86 mA·h/g. The results show that the special“hydrangea”hollow structure can effectively increase the surface area of Nb2O5, thus enabling the hollow C/Nb2O5 microsphere anode material to be characterized with a high specific capacity and good reversible performance.