We studied the dependence between properties and synthesis method for PEGylated ZnS nanoparticles. Thus, we proposed the PEGylation of ZnS nanopowder, in non-aqueous medium, by a facile one-pot synthesis in very mild conditions, as an alternative for the chemical precipitation of PEGylated ZnS in an aqueous solution, and we compared the properties of zinc sulfide obtained by both methods. The structure and morphology of PEGylated ZnS nanopowders were investigated by X-ray diffraction and transmission electron microscopy, and the FTIR spectra confirmed the PEGylation of ZnS nanoparticles. The values for band gap energy are in good accordance with the quantum confinement effect for nanocrystals. The mean dimension of particles was calculated, on the basis of UV–Vis spectra, by using the Brus equation and it is in good agreement with the crystallites size, determined from X-ray diffraction. The photocatalytic properties of synthesized nanopowders were tested in the degradation of Congo red azo dye, demonstrating a faster bleaching of dye in the presence of PEGylated ZnS prepared in non-aqueous medium. The photoluminescence properties are also dependent on the synthesis method and can be correlated with the surface modifications by PEG.