Self-assembed microspheres formed from single-crystal α-MnO2 nanotubes have been successfully synthesized by a facile hydrothermal treatment of KMnO4 in the hydrochloric acid solution. The effect of the reaction time on the microstructure and morphology of the sample is investigated systemically. Meanwhile, the forming mechanism of nano-structured α-MnO2 is carefully studied by X-ray powder diffraction, field emission scanning electron microscopy, transmission electron microscopy and high-resolution transmission electron microscopy. The MnO2 nanotube microspheres exhibit large reversible capacity up to 807 mA h g–1 as well as good cycling stability and rate capability, making them promising as anode material for lithium-ion batteries.