The emergence of graphene has opened the prelude of extensive research on 2D layered materials. Especially, the diverse crystal structures and exceptional physical properties of multielement van der Waals semiconductors have provided a brand‐new platform for the implementation of novel optoelectronic devices. In this study, for the first time, the optoelectronic properties of a newly emerged quaternary van der Waals semiconductor, namely silver indium phosphorus sulfide (AgInP2S6), have been systematically investigated. It is revealed that the AgInP2S6 photodetector exhibits a fast response rate with the response/recovery time down to ≈1/2 ms. In addition, the AgInP2S6 device demonstrates stable photoswitching operation even under a high working temperature of up to 160 °C in the ambient environment without using any specific protection means, and the photoswitching characteristic is also well reserved after a 10‐h continuous heating at 150 °C in air. Profiting from the strong immunity to environmental thermal disturbance, a proof‐of‐concept high‐temperature optical communication application is demonstrated. In conclusion, this study provides an intriguing paradigm for the realization of the next‐generation optoelectronic devices against extreme working circumstances, which contributes to further broadening the scope of application of 2D material photodetectors in the upcoming future (e.g., space communication and tracking).