The chirality of a gold nanocluster can be generated from either an intrinsically chiral inorganic core or an achiral inorganic core in a chiral environment. The first structural determination of a gold nanocluster containing an intrinsic chiral inorganic core is reported. The chiral gold nanocluster [Au20(PP3)4]Cl4 (PP3=tris(2‐(diphenylphosphino)ethyl)phosphine) has been prepared by the reduction of a gold(I)–tetraphosphine precursor in dichloromethane solution. Single‐crystal structural determination reveals that the cluster molecular structure has C3 symmetry. It consists of a Au20 core consolidated by four peripheral tetraphosphines. The Au20 core can be viewed as the combination of an icosahedral Au13 and a helical Y‐shaped Au7 motif. The identity of this Au20 cluster is confirmed by ESI‐MS. The chelation of multidentate phosphines enhances the stability of this Au20 cluster.