Zinc oxide (ZnO) nanostructures with various morphologies have been fabricated in literature owing to their potential applications in various emerging fields. In this study, we report a facile, one-step gram-scale synthesis of nanocrystalline mesoporous ZnO microspheres by thermal decomposition of zinc acetate dihydrate in ethylene glycol at 250 degrees C for 12 h. The average size of the hollow microspheres is found to be 3.01 +/- 0.52 mu m, which are formed by loosely bonded nanocrystallites with average sizes of 17 +/- 4 nm. We propose a formation mechanism for the mesoporous microspheres, Ostwald ripening of spherical-like nanocrystallites, on the basis of the results obtained by different synthesis durations. We also report the possibility of tuning the morphologies of the obtained ZnO by simply modifying the thermal decomposition solution, where porous ZnO nanoplates are obtained when a mixture of ethylene glycol and water is used and ZnO nanorods with aspect ratios of similar to 3 are synthesized by using diethylene glycol. ZnO nanowires with lengths up to several microns are fabricated when no solvent is used, i.e. thermal decomposition in air atmosphere. Microstructural and phase characterizations of the samples are conducted by using a field-emission gun scanning electron microscope and X-ray diffractometer. Performances of the obtained nanocrystalline mesoporous ZnO microspheres in photocatalytic degradation of Rhodamine B and as active anode materials in lithium-ion batteries are also presented. (C) 2018 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.