This article presents a facile surfactant-assisted route to the fabrication of ZnS hollow spheres with diameter of about 0.5∼1 µm in ethanol at room temperature. The surfactant quaternary ammonium salt of 2-undecyl-1-dithioureido-ethyl-imidazoline (SUDEI) prepared in our lab acts as surface-modifying agent, morphology-controlling agent and stabilizing agent in the whole procedure. TEM, SEM, XRD, EDXA, UV-vis, and FTIR were used to characterize the ZnS products. The influences of reaction conditions were discussed while a formation mechanism was proposed to explain this peculiar morphology. The ZnS hollow spheres product is of excellent dispersion capacity and stability in liquid paraffin (LP) and the tribological properties of LP containing ZnS hollow spheres were studied with an Optimol SRV (SRV is the abridged name for German Schwingung, Reibung, Verschleiss) oscillating friction and wear tester, showing excellent anti-wear and friction-reducing performances. The action mechanism of the ZnS hollow spheres in LP was also investigated and discussed.