In this work, α-MoO3 nanoparticles are grown on the surface of nitrogen doped carbon nanotubes (N-CNTs) via a facile electrodeposition method. The morphology of as-prepared nanocomposite shows that the interconnected α-MoO3 nanoparticles are homogeneously distributed on the surface of N-CNTs. When investigated as a cathode material for lithium ion batteries, the nanocomposite reveals a high reversible discharge capacity of 250 mA h g−1 at a current density of 30 mA g−1, simultaneously with good cycling performance and excellent rate capability compared with pristine MoO3 powder. Kinetics of this process is investigated by electrochemical impedance spectroscopy to understand the difference in electrochemical performance and the interface properties between the α-MoO3/N-CNTs nanocomposite and pristine MoO3 powder electrode. The correlation between the unique structural features of α-MoO3/N-CNTs nanocomposite and its excellent electrochemical performance is also discussed. The excellent performance makes the as-prepared α-MoO3/N-CNTs nanocomposite a promising cathode material for high-performance lithium ion batteries.