High crystalline ZnO with hexagonal dumbbell-like bipods morphology was successfully synthesized via N-cetyl-N,N,N-trimethyl ammonium bromide (CTAB)-assisted hydrothermal microemulsion route. X-ray diffraction, scanning electron microscopy, photoluminescence spectrum and Ultraviolet and Visible absorption spectroscopy were used to characterize the structure, morphologies and properties of the as-prepared samples. The results demonstrated that the hydrothermal reaction time had obvious influence on the shape and size of the ZnO products. The Ultraviolet and Visible absorption spectra indicated that the as-prepared ZnO had a strong and broad absorption band from ultraviolet to visible region. The photoluminescence spectra of the synthesized ZnO exhibited a very strong UV emission at similar to 380 nm, indicative of their high crystal quality. Meanwhile, the possible growth mechanism for the formation of hexagonal dumbbell-like ZnO microstructures was proposed. (C) 2011 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.