A facile ultrasonic spray pyrolysis method, without any template and organic additive assistance, was demonstrated to synthesize porous Co3O4 microspheres. The X-ray diffraction (XRD) pattern confirmed that this material was pure Co3O4, and the scanning electron microscopy (SEM) images illustrated the porous microsphere morphology of the as-obtained powders. When performed as anode materials for lithium-ion batteries (LIBs), the as prepared Co3O4 material exhibited remarkable cyclic performance with a reversible capacity of 1073 mA h g−1 after 50 cycles at a current density of 50 mA g−1. Moreover, it retained superior rate performance with the highly reversible capacity of 654 mA h g−1 at the current density of 400 mA g−1.