The self-activated (SA) luminescence in ZnS nanoparticles was studied by comparing the UV-light irradiation induced spectral change, Raman spectra, and EPR spectra of the un-rinsed and rinsed samples. The results show that the SA centers prefer to occupy the sites near the surface and that the donor of SA emission may be related to organic functional groups such as -OH, -CH 3, and -COO. The EPR signals are enhanced remarkably in the rinsed nanoparticles comparing with that in the un-rinsed ones. It is believed that organic functional groups physically combine with the surface dangling bonds of ZnS nanoparticles, leading the nonradiative transition channels to decrease, and thus the SA emission to increase.