Monodisperse PbS hollow spheres were successfully prepared via using CdS aggregate spheres as template. The present strategy is based on the different solubilities of CdS and PbS. This process was intensively studied by time-dependent trails which were monitored by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and photoluminescence spectroscopy (PL). Reaction temperature was found to play an important role in controlling the diffusion rate of Pb2+ ions and the quality of as-prepared PbS crystals, which finally leads to different shape evolution processes from the starting aggregate spheres to the final hollow spheres. Two growth mechanisms defined as kinetics-controlled process (KCP) and thermodynamics-controlled process (TDCP) were, respectively, proposed for the two conversion patterns observed at 30 and 90 A degrees C. Moreover, specific structural evolution including primary crystal size, diameter growth, and shell thickness were also discussed in detail. This work is of great significance in elucidating the underlying mechanism of chemical conversion and could be potentially applied to synthesize other hollow architectures.