Novel uniform-sized, core-shell ZnO mesocrystal microspheres have been synthesized on a large scale using a facile one-pot hydrothermal method in the presence of the water-soluble polymer poly(sodium 4-styrenesulfonate). The mesocrystal forms via a nonclassical crystallization process. The intrinsic dipole field introduced by the nanoplatelets as a result of selective adsorption of the polyelectrolyte on some polar surfaces of the nanoparticles acts as the driving force. In addition, it plays an important role throughout the mesoscale assembly process from the creation of the bimesocrystalline core to the apple-like structure and finally the microsphere. Our calculation based on a dipole model confirms the dipole-field-driven mechanism forming the apple-like structure.