Precise thiolate-protected gold nanocluster, as an ultra-small and multifunctional material, has attracted large interest. The flexibility of gold-sulfur interface forms the basis for the further modification of nanocluster, especially for the ligand exchange reactions (LERs). As a post-synthesis method, LERs offers huge, desired possibilities to the nanoclusters. In this thesis, we investigate the stereoelectronic properties from ligand and whole cluster during exchange process. As a global effect, the stereoelectronic property will induce significant discrimination to the LERs. In addition, ligand exchange induced transformation of nanocluster also involved. Apart from the exchange between cluster and free ligand, we also demonstrated the intercluster ligand exchange with dithiol ligand. We proved that the dithiol ligand didn't desorb from the cluster during the intra/inter dynamic process. More interesting, the Intra/inter dynamic process with chiral ligand will lead to amplification of enantiomeric excess of the cluster system at high temperature.