A pair of enantiopure Au-13 nanoclusters have been enantioselectively synthesized by chiral ligands with stereogenic centers at the phosphorus atoms. Their structures are determined by X-ray crystallography, which are typical models with a high symmetric core and chiral surface ligand arrangement. Correlation between the crystallographic structure, the calculation, and the circular dichroism (CD) study indicates that helical ligand arrangement inducing the core into chiral distortion accounts for the chiroptical activities in the visible region. A rare example of cocrystallization of a mixture of diastereomers has been observed for the first time for gold nanoclusters, reflecting the lack of chiral self-sorting of the ligands.