High-quality ZnO single crystals of dimensions 10×10×0.3 mm3, grown either using a pressurized melt or a hydrothermal growth approach, have been investigated in their as-received state and are compared regarding their properties revealed by positron annihilation and Hall effect measurements. By positron annihilation performed at room temperature it is found that the pressurized melt grown crystals contain a certain amount of Zn+O divacancies, but no Zn vacancies are detected, whereas the hydrothermally grown crystals contain a dominating defect yet unknown in its structure but possibly connected to the Zn vacancy. Furthermore, the influence of an additional refined chemical–mechanical polishing of the crystal surface by a special procedure on the depth distribution of vacancy-type defects is demonstrated. Hall measurements, performed in the temperature range 20–325 K, showed that the crystal growth method has a strong influence on the carrier mobility, and the estimated acceptor densities also differ significantly in both types of crystal.