The controlled synthesis of PbS nanostructures with crystal morphology of hierarchical submicron cubes has been realized by chemical synthesis between lead acetate trihydrate and sulfur via a solvothermal route. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy were used to characterize the products. It was shown that well-dispersed and hierarchical PbS submicron cubes were formed at low temperature. Experiments demonstrated that the morphologies of PbS crystals were significantly influenced by treatment temperature, reaction time, and sulfur sources. A growth model was proposed for the selective formation of hierarchical PbS submicron cubes. Our work demonstrated the growth of hierarchical PbS architectures through a one-step, surfactant-free and solution-phase chemical route under controlled conditions.