Co3O4, a type of transition metal oxide, is known as a promising anode material for high-performance Li-ion batteries (LIBs), attracting wide research attention because of its high theoretical specific capacity, high tapped density as well as stable chemical properties. In this review, we first discuss the synthesis of pure Co3O4 with different morphologies, such as 1D nanostructures (nanorods and nanowires), 2D nanostructures (nanosheets), 3D nanostructures (nanocubes, nanoboxes, polyhedral and fusiform nanostructures), and multistage nanostructures (flower-like nanostructures). Then, we focus on the application of pure Co3O4 and its composites, such as Co3O4/C, Co3O4/graphene, and Co3O4/metal oxide, in LIBs.