Zinc oxide (0001) bulk crystals were implanted by 100 keV H2+ ions with various fluences in the range of 5×1016 to 3×1017 cm–2. Surface layer exfoliation was observed in the case of samples that were implanted with fluence higher than 2.5×1017 cm–2, either in the as‐implanted state or after annealing at higher temperatures up to 500 °C. The roughness of the exfoliated surfaces, as measured using atomic force microscopy, was found to be about 20 nm. These samples with exfoliated surfaces were further annealed at higher temperatures up to 1000 °C under air atmosphere. The surface morphology of the samples was studied using Nomarski optical microscopy, scanning electron microscopy (SEM) and atomic force microscopy (AFM). The defect characterization in the implanted ZnO samples was performed using transmission electron microscopy (TEM). Cross‐sectional TEM measurements showed the formation of hydrogen filled nanovoids inside the damage band in ZnO. It was observed that after annealing the samples at 960 °C for 1 hr in air ambient, the roughness of the exfoliated surfaces reduced down to about 3 nm. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)