Chalcogenide (ChG) glasses with micro-nano structure arrays are increasingly demanded in infrared optical systems owing to their excellent antireflective properties, and can be mass-produced by precision glass molding (PGM). Nickel-phosphorus (Ni–P) plated molds are commonly used in the PGM process, but the Ni atoms tend to react with the ChG glass at high temperatures. In this study, we propose a novel two-step PGM process. A Ni–P mold is used to transfer antireflective micro-nano structure array to silicate glass. Then the silicate glass, which has a higher glass transition temperature (Tg) than the ChG glass, is used as the mold to replicate the antireflective structured surface to the ChG glass. The results show that the ChG glass micro-nano structure array has high forming accuracy and favorable infrared optical transmission characteristics. The silicate glass is proved to be an appropriate mold material for the ChG glass molding process. This work provides a novel type of the PGM techniques for ChG glass materials.