Hierarchical urchin-like hollow spheres (5–8 μm in diameter) assembled by one-dimensional nanowires consisting of many interconnected Co3O4 nanoparticles (10–50 nm) are successfully synthesized. Co(CO3)0.5(OH)·0.11H2O precursors are firstly prepared by a hydrothermal process. The morphological evolution process of Co(CO3)0.5(OH)·0.11H2O hollow urchin precursors is investigated and a plausible mechanism is proposed. Then, the Co(CO3)0.5(OH)·0.11H2O are converted to Co3O4 through heat treatment in air. As an anode material for lithium ion batteries, urchin-like Co3O4 hollow spheres exhibit highly reversible specific capacities, good cycling stabilities and excellent rate capabilities (e.g., 433 mAh g−1 at 10 C). The superior performances result from the synergetic effect of integral urchin-like microstructure, small diffusion lengths in the nanoparticle building blocks and sufficient void space to buffer the volume expansion.