We report high-efficiency CdTe/CdS core/shell nanocrystals synthesized in water by epitaxially growing CdS shells on aqueous CdTe cores at room temperature, enabled by the controlled release of S species under low-intensity ultraviolet (UV) light illumination. The resulting photo-induced dissociation of S2O32− ions conveniently triggers the formation of critical two-dimensional CdS epitaxy on the CdTe surface at room temperature, as opposed to initiating the growth of individual CdS core-only nanocrystals. This controlled colloidal hetero-epitaxy leads to a substantial increase in the photoluminescence (PL) quantum yield (QY) of the shelled nanocrystals in water (reaching 64%). With a systematic set of studies, the maximum PL QY is found to be almost independent of the illuminating UV intensity, while the shell formation kinetics required for reaching the maximum QY linearly depends on the illuminating UV intensity. A stability study of the QD films in air at various temperatures shows highly improved thermal stability of the shelled QDs (up to 120 °C in ambient air). These results indicate that the proposed aqueous CdTe/CdS core/shell nanocrystals hold great promise for applications requiring efficiency and stability.