Carbon-coated Li₂MoO₄ hexagonal hollow nanotubes were fabricated via a facile sol–gel method involving the solution synthesis of Li₂MoO₄ with subsequent annealing under an inert atmosphere to decompose the organic carbon source. To the best of our knowledge, this is the first report on the synthesis of Li₂MoO₄ nanotubes. More significantly, we have found that Li₂MoO₄ can be used as an anode material for lithium-ion batteries (LIBs). When evaluated as an anode material, the carbon-coated Li₂MoO₄ hollow nanotubes show an excellent electrochemical performance with a high reversible capacity (∼550 mA h g⁻¹) after 23 cycles, good rate capability and cycling stability. Meanwhile, carbon-free Li₂MoO₄ sample, fabricated via a solid state reaction, was also prepared for comparison. The Li storage mechanism has been investigated in-detail by advanced XPS, in situ XRD and HRTEM.