CaWO4 and SrWO4 nanostructures have been synthesized via a simple microemulsion-mediated route. With careful control of the fundamental experimental parameters including the concentration of reactants, the reaction time and the temperature, the products with different morphologies of dumbbell, coral, rod and dendrite have been obtained, respectively. The possible formation mechanism of these unique morphologies has been proposed based on surfactant self-assembly under different experimental conditions. The as-synthesized CaWO4 samples with various morphologies exhibit different photoluminescence properties. X-ray powder diffraction, transmission electron microscopy, field-emission scanning electron microscopy, and luminescence spectroscopy were used to characterize these products. Crown Copyright (C) 2008 Published by Elsevier Ltd. All rights reserved.