In this work, a novel lead sulfide (PbS) hierarchical superstructure, denoted as octapodal dendrites with a cubic center, has been synthesized employing a simple single-source precursor route. Our experimental results demonstrate that the novel hierarchical superstructure was generated through the delicate balance between the kinetic growth and thermodynamic growth regimes. Moreover, the morphology of PbS crystals can be controlled by adjusting the solvent under a thermodynamically or kinetically controlled growth regime. It is highly expected that these findings will be useful in understanding the formation of PbS nanocrystals with different morphologies, which are also applicable to other face-centered cubic nanocrystals.