Anisotropic column-shaped porous Co3O4 nanocapsules were successfully synthesized via a solvothermal route using poly(vinyl pyrrolidone) (PVP) as capping reagent and final heat treatment in air. These anisotropic polycrystalline nanocapsules with the length of ∼1 μm and the diameter of ∼400 nm were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) methods. Detailed proof indicated that the process of CoCO3 precursor growth was dominated by a nucleation and growth, self-organization, and then Ostwald ripening growth mechanism. These column-shaped Co3O4 nanocapsules integrate two beneficial features: hollow cavity and porous shell. When evaluated for Li-ion batteries, they exhibit high reversible capacity (over 1000 mA h g−1) and good cycle performance.