Precision glass molding (PGM) has become an efficacious technique to fabricate high-precision optics. Chalcogenide (ChG) glass is increasingly used in thermal imaging, night vision, etc., because of its excellent infrared optical properties. Nevertheless, glass-mold interfacial adhesion has emerged as a pivotal issue within the PGM process. The interfacial adhesion during PGM has the potential to significantly undermine the performance of molded optics and reduce the longevity of molds. It is important to investigate interfacial adhesion behaviors in the PGM. In this study, the interfacial adhesion mechanism between ChG glass and the nickel-phosphorus (Ni-P) mold is analyzed using the cylindrical compression test. The effect of ChG glass internal stress on physical adhesion is investigated by finite element method (FEM) simulation. The spherical preform is proven to be capable of reducing the stress concentration and preventing physical adhesion. More importantly, a rhenium-iridium (Re-Ir) alloy coating is deposited on the Ni-P mold surface by ion sputtering to prevent atomic diffusion and resolve the problem of chemical adhesion. Finally, ChG glass microstructures with high accuracy are fabricated using the spherical ChG glass preform and the Re-Ir-coated Ni-P mold by PGM.