ZnWO4:Eu nanorods were characterized by SEM, TEM, XRD and Raman spectroscopy. The optical properties were investigated by UV–vis and photoluminescence spectroscopy. The temperature-dependent structure and optical properties of ZnWO4:Eu nanorods have been investigated. It was found that temperature-induced monoclinic phase to molten state transition occurred at 1573 K. The ZnWO4 intrinsic luminescence and Eu3+ emission intensities decreased rapidly with the increase of temperature. Copyright © 2014 John Wiley & Sons, Ltd.