Large-scale arrayed ZnO crystals with a series of novel morphologies, including tower-like, flower-like, and tube-like samples, have been successfully fabricated by a simple aqueous solution route. The morphology and orientation of the obtained ZnO crystal arrays can be conveniently tailored by changing the reactants and experimental conditions. For example, the tower-like ZnO crystal arrays were obtained in a reaction solution system including zinc salt, ammonia, ammonium salt, and thiourea, and the orientation of these tower-like crystals could be controlled by the contents of these reactants. Flower-like ZnO arrays were obtained at lower temperatures, and tube-like ZnO arrays were obtained by ultrasonic pretreatment of the reaction system. The growth mechanism of the tower-like and tube-like ZnO crystals was investigated by FESEM. The results show that tower-like crystals grow layer by layer, while tube-like crystals grow from active nanowires. Ultrasonic pretreatment is proved to be effective in promoting the formation of active nuclei, which have important effects on the formation of the tube-like ZnO crystals. In addition, large-scale arrays of these ZnO crystals can be successfully synthesized onto various substrates such as amorphous glass, crystalline quartz, and PET. This implies this chemical method has a wide application in the fabrication of nano-/microscale devices.