Porous Nb2O5 spheres are to be synthesized in a calcination and hydro-thermal process, with its template the surfactant cetyltrimethyl-ammonium chloride (CTAB). Testing results of the characterization and electrochemical properties of the finished products show that a successful synthesis of orthorhombic Nb2O5 spheres can be obtained with a better dispersion performance. About 900 nm in diameter, the spheres are distributed with many porous of 2~70 nm in aperture, and its unique porous structure helps to increase the specific surface area (as large as 340 m2/g). As an anode material for lithium-ion batteries, the unique porous structure and relatively large specific surface area contribute to its excellent electrochemical properties: with an initial charge of 297.8 and a discharge capacity of 395.9 mA·h·g-1, respectively; stable in its cycling performance, with its coulombic efficiency as high as 100% at the current density of 20 mA/g after the 3rd cycle; excellent in its magnification performance, with a capacity of 139.6 mA·h·g-1 at 50 mA/g, and 117.1 mA·h·g-1 at 100 mA/g. Meanwhile, the capacity retention at the current density of 50 and 100 mA/g reaches as high as over 90% after the 20th cycle. These results indicate that porous Nb2O5 spheres show a high reversible charge/discharge capacity, stable cycling performance and high rate capability.