A fundamental understanding of the luminescence of Au-thiolate nanoclusters (NCs), such as the origin of emission and the size effect in luminescence, is pivotal to the development of efficient synthesis routes for highly luminescent Au NCs. This paper reports an interesting finding of Au(I)-thiolate complexes: strong luminescence emission by the mechanism of aggregation-induced emission (AIE). The AIE property of the complexes was then used to develop a simple one-pot synthesis of highly luminescent Au-thiolate NCs with a quantum yield of ~15%. Our key strategy was to induce the controlled aggregation of Au(I)-thiolate complexes on in situ generated Au(0) cores to form Au(0)@Au(I)-thiolate core-shell NCs where strong luminescence was generated by the AIE of Au(I)-thiolate complexes on the NC surface. We were able to extend the synthetic strategy to other thiolate ligands with added functionalities (in the form of custom-designed peptides). The discovery (e.g., identifying the source of emission and the size effect in luminescence) and the synthesis protocols in this study can contribute significantly to better understanding of these new luminescence probes and the development of new synthetic routes.