Sb(III)-doped lead tungstate single crystals with controlled shapes and enhanced green emission have been synthesized via a facile, Pluronic P123 (EO20PO70EO20)-assisted, sonochemical method. The surfactant Pluronic P123 was found to play a crucial role in the morphology control of the final products. The growth process was investigated by carefully following time-dependent experiments, and the oriented attachment process accompanying Ostwald ripening was proposed for the possible formation mechanism. The optical properties, such as the Raman spectra and PL spectra, of doped PbWO4 were studied. Room-temperature photoluminescence of doped PbWO4 samples with different morphologies at desired Sb doping concentrations showed greatly enhanced luminescence intensity compared to the undoped PbWO4.