Lead tungstate (PbWO4) microcrystals were synthesized for the first time, via different concentrations of PVA assisted sonochemical process. The concentration of PVA acts as a structure directing agent and played an important role in the morphological control of resulting PbWO4 microcrystals. The product PbWO4 composing of Pb, W and O and WO stretching vibration band of WO4 tetrahedrons were confirmed through XRD, FTIR, FESEM and EDS. The TG/DTA curves showed that the particles are crystallized at room temperature itself and the thermal stability of the product is really good. The optical properties of the product shows extraordinarily high room temperature photoluminescence intensity compared to without PVA assisted product.