The transformation pathways in cluster regions have received only limited attention, and the fundamental issues involved require in-depth study. Here, we demonstrate the formation and transformation mechanisms in Cd-based MSCs by studying spectroscopically pure (CdS) 13 MSCs. We show that the molecular formula of the obtained CdS MSCs is [(CdS) 13 (RNH 2 ) 13 ] and that the experimental estimate of the diameter is approximately 0.75 nm. Further study reveals that, in addition to the amine-bilayer templated synthesis route, two other transformation pathways exist in the semiconductor cluster region. Pathway 1 involves intercluster transformation and undergoes a process of dissolution and regrowth, while Pathway 2 is an anion exchange reaction. The latter is considered to be difficult in nanocrystal synthesis and is observed for the first time in semiconductor MSCs. The present findings not only enrich the cluster family but also provide profound insight into the transformation mechanisms between MSCs, which will further shed light on the synthesis of nanocrystals.