Undoped, Mn-doped, Pr-doped, and Mn- and Pr-codoped ZnS nanoparticles were synthesized by a wet chemical method, and these nanoparticles were optically annealed in air or vacuum. In the photoluminescence (PL) spectra of the optically annealed nanoparticles, a sulfur-vacancy-related PL band at around 420 nm, a PL band associated with the T-4(1) -> (6)A(1) transition of Mn2+, and PL peaks associated with Pr-related complexes were investigated during optical annealing. The integrated PL intensities for the nanoparticles annealed in air increased more markedly with the optical annealing time than those for the nanoparticles annealed in vacuum. This increase may be explained by the photooxidation of the surface, the enhancement of the crystal quality, and the gradual diffusion of luminescent ions into the crystal lattice.