The composite of manganese monoxide and multi-walled carbon nanotubes (MnO/MWNTs) is prepared hydrothermally by MWNTs and KMnO4 followed with a sintering process. After reducing KMnO4 as the reductant, the leftover MWNTs are found randomly distributed in the final MnO rods forming a conducting network. More importantly, they can buffer the volume change of MnO during lithium incorporation/extraction. As a result, the rate capability and cycling performance of MnO as an anode material for lithium ion batteries are significantly improved. The MnO/MWNTs composite shows a reversible capacity as high as 770.6 mA h g−1 and 455.3 mA h g−1 at the current density of 7.21 mA g−1 and 310.23 mA g−1 respectively between 0.01 and 3.5 V (vs. Li/Li+ hereafter). Furthermore, the capacity retention is over 92.4% after 200 cycles at 216.14 mA g−1 between 0.01 and 3.0 V.