Superposed cobalt(II)-cobalt(III) layered double hydroxide (Co(II)-Co(III)-LDH) nanoplates were synthesized by an oil droplet template method, in which the main steps are as follows: LDH nanosheets were first assembled on an oil droplet template to form a multishell sphere, and then the oil droplet was easily removed under centrifugal force due to its very different density from that of the assembled LDH shell. This resulted in the multishell spheres being split open to create superposed LDH nanoplates. The resulting material has a three-stage architecture, namely, the primary building blocks of nanosheets, the secondary architecture of shells derived from the nanosheets, and the long-range architecture of superposed nanoplates assembled from the vertically stacked shells. Most importantly, the as-fabricated LDH-based hierarchical structure can be readily converted to a Co3O4/C composite via calcination, without obvious structural alteration, where the residual surfactant is the source of the carbon. When used as an anode material for Li-ion batteries, the Co3O4/C electrode exhibits an excellent electrochemical performance, which is attributed to the unique hierarchically porous structure.