Novel nanosized lead tungstate (PbWO4) hollow spindles were successfully synthesized, for the first time, via a Pluronic P123-(EO20PO70EO20-) assisted sonochemical process. The triblock copolymer acted as a structure-directing agent and played a key role in the formation of the hollow spindles. An in situ micelle templating mechanism has been proposed for the possible formation mechanism of the hollow nanostructure. The optical properties of the final products were investigated. It is exciting that the as-prepared PbWO4 hollow structure shows extraordinarily high room-temperature photoluminescence intensity compared to the solid structures.