A uniform hierarchical mesoporous Co3O4@C-N nanostructure rods were in situ fabricated successfully by developing a facile one-step strategy. Cobalt-based metal organic framework [Co3(ndc)(HCOO)3(μ-OH)(H2O)]n with special Co chine constructed framework structure treated as a precursor directly pyrolyzed in a mixed atmosphere of argon and oxygen (95:5) at 500 °C for 2 h. According to the XRD pattern, SEM, TEM, EDS mapping images and XPS spectrum analysis, the well-defined hierarchical mesoporous Co3O4@C-N nanostructure rods showed pure Co3O4 phase, are assembled from a large number of core–shell structured Co3O4@C-N spherical particles with an ultrasmall and uniform size (∼8 nm) which were further connected by N doped carbon net to form nanostructure rods. Using as anode material for lithium-ion batteries, these hierarchical mesoporous Co3O4@C-N nanostructure rods exhibit excellent electrochemical performance with high reversible capacity, rate capability and good cycling stability. They maintained a reversible specific capacity of more than 1000 mAh/g at 100 mA/g, and the discharge specific capacities at the 5 current density of 0.1, 0.2, 0.5, 1, 2, and 5 A/g reached 1123, 1094, 1044, 979, 879 and 688 mAh/g, respectively.