By employing chiral precursors, a new class of chiral gold(I) sulfido clusters with unique structures has been constructed. Interestingly, pure enantiomers of the precursors are found to self-assemble into chiral hexaand decanuclear clusters sequentially, while a racemic mixture of them has resulted in heterochiral self-sorting of an achiral mesa decanuclear cluster. Chirality has determined not only the symmetry and structures but also the photophysical behaviors of these clusters. The racemic mixture of decanuclear clusters undergoes rearrangement and heterochiral self-sorting to give a meso decanuclear cluster. The thermodynamic-driven heterochiral self-sorting of gold(I) clusters provides a means to develop controlled self-assembly that may be of relevance to the understanding of chirality in nature.