A large scale direct thermal decomposition method has been developed to prepare NiO/MWCNT nanocomposites. The as-prepared NiO nanoparticles are uniformly coated onto the surface of MWCNTs. The well crystallized NiO/MWCNT composites show superior electrochemical performance in Li ion batteries. The lithium storage capacity maintains at ∼800mAhg−1 after 50 discharge/charge cycles, which is much larger than those reported for NiO and its composites. Therefore, the NiO/MWCNT composites have significant potentials for application in energy storage devices. The direct thermal decomposition method is a versatile route for preparing carbon nanotube-inorganic hybrid electrode materials for lithium ion batteries.