The synthesis of macrostar-like PbS hierarchical structures by a simple hydrothermal method at 180 degrees C for 24 h is proven successful with the assistance of a new surfactant called tetrabutylammonium bromide (TBAB). The as-obtained product is characterized by means of X-ray powder diffraction, field emission scanning electron microscopy, energy dispersive spectrometry, high resolution transmission electron microscopy, and selected area electron diffraction. The presence of TBAB and NaF plays an important role in the formation of PbS macrostructures. Ostwald-ripening-assisted oriented attachment is believed to play a key role in the growth behavior of novel 3D structures. As such, a possible self-assembly mechanism is proposed to explain the formation of the said structures. The present study aims to introduce new insights into understanding the formation process of such unique hierarchical superstructures. (C) 2011 Elsevier Ltd. All rights reserved.