Hydrozincite (Zn-5(CO3)(2)(OH)(6)) microspheres with a tunable surface architecture have been successfully synthesized via a homogeneous precipitation method under solvothermal conditions. For a smooth hydrozincite microsphere, various building blocks such as nanocubes, nanorods, and nanosheets are arranged to cover a spherical surface by concisely controlling reaction time and the volume of ethylene glycol. Hexagonal Zn-5(CO3)(2)(OH)(6) with nanostep structures are also prepared without any additives. The hollow ZnO microspheres with a porous surface have been successfully fabricated via a solution-based method by the room-temperature treatment of filled Zn-5(CO3)(2)(OH)(6) microspheres composed of nanocubes. A possible growth mechanism of these hollow ZnO microspheres is proposed. The similar filled ZnO microspheres can also be obtained by a direct pyrolysis of Zn-5(CO3)(2)(OH)(6) microspheres composed of nanocubes at 450 degrees C.