In this study, we fabricated ZnS substrates with excellent transmittance in the mid-infrared region (3–5 µm) using hot pressing instead of conventional chemical vapor deposition (CVD). Diamond-like carbon (DLC) was coated on either one or both sides of the ZnS substrates to improve their mechanical properties and transmittance efficiency. To reduce the reflectance and further improve transmittance in the mid-infrared region, anti-reflection (AR) coating was designed for DLC/ZnS /AR and AR/ ZnS /AR structures. The coating structure, microstructure, and optical properties of the AR-coated ZnS substrates were subsequently investigated by employing energy dispersive X-ray spectroscopy, scanning electron microscopy, and Fourier-transform infrared (FTIR) spectroscopy. The FTIR spectroscopy results demonstrated that, in the mid-infrared region, the average transmittance of the samples with AR coating on one and both sides increased by approximately 18% and 27%, respectively. Thus, AR coating improved the transmittance of the ZnS substrates.