Vertically aligned mesoporous carbon nanotubes (MCTs) filled with Co3O4 nanoparticles (NPs) were fabricated by a dual template method; a hard template-assisted sol–gel process. The Co3O4/MCT electrode was characterized by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. The data indicate that the Co3O4 NPs are dispersed uniformly on the inside surface of the MCT. As an anode material for a Li ion battery, the resulting electrode shows a high reversible capacity of about 627mAhg−1 after the 50th discharge. The improved electrochemical performance of Co3O4/MCT can mainly be attributed to the small-size Co3O4 NPs and the rapid diffusion of Li-ions induced by the three-dimensional structure of the MCT. The Co3O4/MCT electrode has the potential for use as a high-performance anode electrode for Li-ion batteries.