Synthesis and characterization of highly luminescent ZnS-passivated CdS:Mn (CdS:Mn/ZnS) core/shell structured nanocrystals are reported. Mn-doped CdS core nanocrystals are produced ranging from 1.5 to 2.3 nm in diameter with epitaxial ZnS shell of wider band gap via a reverse micelle process. UV irradiation-stimulated photo-oxidation of the ZnS shell results in formation of sulfate (ZnSO4) as determined by x-ray photoelectron spectroscopy, which increases the photoluminescence emission intensity and subsequent photostability. Luminescent relaxation lifetime data present two different decay components, consisting of slow decay emission from the Mn center and a fast decay emission from a defect-related center. The impact of the density of surface defect states upon the emission spectra is discussed. (C) 2004 American Institute of Physics.