Anionic surfactant-AOT-microemulsions-assisted formation and evolution of PbWO4 nanostructures with bundles rodlike, ellipsoidlike, and spherelike prepared at different media conditions were studied by powder X-ray diffraction pattern, field emission scanning electron microscopy, and transmission electron microscopy. The possible mechanisms for the formation of PbWO4 samples in series of microemulsion systems were discussed. Various comparison experiments show that several experimental parameters, such as the AOT concentration, the water content, and reaction temperature play important roles in the morphological control of PbWO4 nanostructures. Room-temperature photoluminescence of PbWO4 samples with different morphologies has also been investigated and the results reveal that all these samples showed similar features with emissions at 480 similar to 510 mn but different luminescence intensity.