Zinc sulfide (ZnS) is one of the most important far-infrared optical candidate materials. However, it is indispensable for ZnS to improve its antireflection and protection especially under harsh environments. Compared with conventional surface antireflective films, surface sub-wavelength structures (SWSs) have some unique advantages. In this paper, dewetting nickel dots as etching mask on ZnS substrates were obtained by thermal annealing of as-sputtered Ni films on the intermediate layers of as-sputtered silicon films. ZnS SWSs were then prepared by inductively coupled plasma (ICP) etching. Finally, HfO2 films were deposited on ZnS SWSs by atomic layer deposition. The influences of SWSs and ALD-derived HfO2 films on the transmittance and protection of ZnS were both investigated. The experimental results show that ZnS SWSs can increase both far-infrared transmittance and surface hydrophobicity. Meanwhile, ALD-derived HfO2 films can provide good protection. Compared with bare ZnS, HfO2-coated ZnS with double-sided SWS exhibits average transmittance of 79.2% other than initial 69.1% in 8-12 mu m, better hydrophobicity with the wetting angle of 119.7 degrees, and higher composite nano-hardness increased from 25.00 to 38.68 GPa. ALD derived HfO2 films on ZnS surface sub-wavelength structures have excellent application prospective for infrared optical windows.