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The sizes and morphologies of hexagonal phase ZnO crystals were successfully controlled by a hydrothermal process in the presence of poly (acrylic acid) (PAA). The dosage of NaOH in this reaction system proved to be crucial in the growth process. With the increase of dosage from 0.7 g to 3.0 g, the morphologies of the ZnO crystals changed from nanoplates to microrods. Their optical properties were also investigated.