Multi-arm PbS architectures were successfully synthesized in high yield by a facile hydrothermal process at 90 °C for 48 h, employing lead nitrate (Pb(NO3)2) and thioacetamide (TAA) as precursors. A new surfactant: tetrabutyl ammonium bromide (TBAB), was used in this process. The as-prepared PbS products are characterized by X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and Fourier transform infrared (FT-IR) spectroscopy. The results showed that the concentration of TBAB, as well as the molar ratio of Pb(NO3)2 to TAA are crucial factors on the morphologies and sizes of the hierarchical PbS microcrystals. A reasonable possible new formation mechanism of hierarchical PbS structures based on the adsorption and sustained release of H2S by TBAB has been presented.Graphical abstractPbS uniform hierarchical microstars were grown on a large scale by a simple hydrothermal method with the help of a new surfactant: tetrabutyl ammonium bromide (C16H36BrN). A possible new formation mechanism of hierarchical hollow PbS structures based on the adsorption and sustained release of S2+ by TBAB is presented.Highlights► Multi-arm PbS hierarchical structures were successfully synthesized by a simple hydrothermal method at low temperature: 90 °C. ► A new surfactant: tetrabutyl ammonium bromide (TBAB) was used in the process, a possible new formation mechanism of hierarchical hollow PbS structures based on the adsorption and sustained release of S2+ by TBAB is presented.