The pyrolysis of metal-organic frameworks (MOFs) is an ingenious way to synthesize carbon-based materials with unique morphology for various applications including electrocatalysis. In this work, we reported a facile morphology regulation strategy for the synthesis of a spherical superstructure of MOF nanosheets. The use of metal hydroxide nanosheets on Zn particles as precursors/templates allowed MOFs with general polyhedron shape to form nanosheets and assemble into a spherical superstructure in the ligand solution. Further, a hollow spherical superstructure of carbon nanosheets decorated with metal-based nanoparticles was fabricated through the pyrolysis of MOF nanosheet superstructures at 950 °C, where the substrate/template Zn particle cores were evaporated away. The obtained composites possess carbon-based superstructures with abundant mesopores and metal-based nanoparticles with rich alloy/oxide interfaces. These features endow this MOF-derived carbon-based material with outstanding bifunctional activity for oxygen reduction/evolution reactions and great performances in Zn-air batteries.