A simple and versatile solvent-growth process using ethylene glycol has been demonstrated for the synthesis of novel faceted bipyramidal zinc glycolate. Upon thermal treatment in air, this structure can be converted into a ZnO hexagonal phase with wurtzite structure via solid-state transformation. The morphology, microstructure, and crystallinity of the products before and after thermal treatment have been characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, and solid-state C-13 NMR measurements. In addition, the room-temperature photoluminescence of the resulting ZnO has also been investigated.