Piezocatalytic materials have been widely used for catalytic hydrogen evolution and purification of organic contaminants.However,most studies focus on nano-size and/or polycrystalline catalysts,suffer-ing from aggregation and neutralization of internal piezoelectric field caused by polydomains.Here we report a single crystal ZnO of large size and few bulk defects crafted by a hydrothermal method for piezo-catalytic hydrogen generation from pure water.It is noteworthy that single-side surface areas of both original as-prepared ZnO and Ga-doped ZnO bulk crystals are larger than 30 cm2.The high quality of ZnO and Ga-doped ZnO bulks are further uncovered by high-resolution transmission electron microscope(HRTEM),photoluminescence (PL) and X-ray diffraction (XRD).Remarkably,an outstanding hydrogen production rate of co-catalyst-free Ga-doped ZnO bulk crystal (i.e.,a maximum rate of 5915 μmol h-1 m-2) is observed in pure water triggered by ultrasound in dark,which is over 100 times higher than that of its powder counterpart (i.e.,52.54 μmol h-1 m-2).The piezocatalytic performance of ZnO bulk crystal is systematically studied in terms of varied exposed crystal facet,thickness and conductivity.Different piezocatalytic performances are attributed to magnitude and distribution of piezoelectric potential,revealed by the finite element method (FEM) simulation.The density functional theory (DFT) calculations are employed to investigate the piezocatalytic hydrogen evolution process,indicating a strong H2O adsorption and a low energy barrier for both H2O dissociation and H2 generation on the stressed Zn-terminated (0001) ZnO surface.