Heterostructures of metal nanoparticles and semiconductors are widely studied for their unique properties. However, few reports are available on the heterostructure of metal nanoclusters and semiconductors. In the present study, a heterostructure, in which gold nanoclusters selectively locate at ZnS quantum rod (QR) tips, was fabricated using a two-step solvothermal route. The composition, intrinsic crystallography, and junction of the prepared heterostructure were thoroughly investigated, and it was observed to exhibit novel luminescent behaviours. By comparison with the individual components of ZnS QRs and gold clusters, the resultant heterostructure shows an enhanced exciton emission and complete depression of defect emission for the ZnS component, and a pronounced red emission for the gold nanocluster component. The mechanism of these properties and the charge transfer between gold nanoclusters and ZnS QRs were also explored. The size and location of gold in the heterostructure were also controlled during synthesis to study their effects on the luminescence.