Large‐scale star‐like PbWO4 hierarchical architectures were controllably synthesized by a facile surfactant‐assisted technology under mild conditions in the presence of a mixed solvent of ethylene glycol and water. The morphology, structure, and phase composition of PbWO4 architectures were characterized by X‐ray diffraction (XRD), field emission scanning electron microscopy (FE‐SEM), field emission transmission electron microscopy (FE‐TEM), and nitrogen adsorption‐desorption isotherms. The possible formation mechanism of the star‐like PbWO4 architectures (initial nucleating stage and a subsequent self‐assembly stage) was proposed based on the observations from a time‐dependent morphology evolution process, which may pave the way to shape‐controlled synthesis of inorganic nanocrystals with the complex structures. This route provides a facile strategy to fabricate complex hierarchical PbWO4 structures. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)