A novel design of 3D porous Ti2Nb10O29 microspheres coated with ultrathin N-doped carbon layers, which can improve electron/ion transport, shows remarkable high-rate capacity (267 mA h g-1 at 10C and 199 mA h g-1 at 40C) and stable cycle lives with a high capacity retention rate of 90.2% after 500 cycles.