The sensitive and selective detection of hydrogen sulfide is of great importance due to its crucial role in pathological and physiological processes. Herein, we report a novel fluorescent platform, AuNCs@GC, for selective detection of hydrogen sulfide in living cells by impregnating the Au nanoclusters (AuNCs) into a biocompatible cationic polymer matrix, glycol-chitosan (GC) nanogel. The confinement effect significantly increased the emissive Au(I) units, resulting in a 6-fold enhancement of quantum yield (from 6.38% to 36.42%). In addition, the prepared positively charged AuNCs@GC nanogel exhibits excellent selectivity and improved sensitivity to aqueous sulfides. Moreover, the as-fabricated AuNCs@GC showed very good biocompatibility and super fluorescence stability across the full pH range and good salt tolerance, which demonstrated excellent adaptability toward intracellular sulfide imaging.