Different Zinc tungstate (ZnWO4) nanostructures were controllably synthesized via facile hydrothermal method in the presence of surfactant polyethylene glycol 20000 (PEG-20000). During the synthesis, cheap and simple inorganic salts were used as precursors. The shape and size of ZnWO4 nano/microstructures can be well controlled by the dosage of surfactant, the pH value of reaction system and other hydrothermal parameters. Apart from structural and morphological characterizations of the ZnWO4 nano/microstructures, the composition and the photoluminescent (PL) properties of typical samples have also been investigated by powder X-ray diffraction pattern and fluorescence spectrophotometer, respectively. The results indicated that all the products of ZnWO4 with different morphologies exhibited the only blue peak at 506 nm with an excitation wavelength at 253 nm.