A facile boiling water synthesis protocol has been developed to synthesize thiolated Ag nanoclusters with a core-shell Ag(0)@Ag(i)-thiolate structure, which was formed through condensation of Ag(i)-thiolate complexes on the surface of an in situ formed Ag(0) core. The as-synthesized thiolated Ag nanoclusters feature strong luminescence via aggregation-induced-emission (AIE).