This study presents a new crystal structure of a gold nanocluster coprotected by thiolate and chloride, with the formula of Au-36(SCH2Ph-Bu-t)(8)Cl-20. This nanocluster is composed of a Aum core with two Cl atoms, a pair of pentameric Au-5(SCl5) staple motifs, and a pair of hexameric Au-6(S3Cl4) motifs. It is noteworthy that the "Au-Cl-Au" staple motifs are observed for the first time in thiolate protected gold nanoclusters. More importantly, the formation of the Cl-Au, motifs is found to be mainly responsible for the configuration of the gold nanocluster. This work will offer a new perspective to understand how the ligands affect the crystal structure of gold nanocluster.