DBS surface-modified nanocrystalline ZnS:Mn was prepared by a precipitation method. Photoluminescence spectra and decay curves were measured and compared to those of unmodified samples. For both kinds of samples, luminescence decay curves of 600 nm emission consist of two components with nanosecond (ns) and millisecond (ms) lifetimes. The nanosecond component is attributed to zinc vacancies luminescence, with peak located at 440 nm. While the millisecond component is attributed to Mn2+ luminescence and its decay time changes with Mn2+ concentration and surface modification. The surface-modified sample has a longer lifetime compared to unmodified samples. The photoaging of surface-modified samples is slow. Particle size effects on photoaging were also examined. For nanocrystalline ZnS:Mn photoaging is more noticeable than that of bulk material. After UV irradiation, photoluminescence intensity of the modified sample is several times larger than that of the unmodified sample, because the surface-active reagent decreases surface defects and depresses radiationless transitions. XPS yields direct evidence of the surface-modification effect on the surface structure.