AbstractMultivalley systems offer not only exciting physical phenomena but also the possibility of broad utilization. Identifying an important platform and understanding its physics are paramount tasks to improve their capability for application. Here, we investigate a promising candidate, the semiconductor SnSe, by optical spectroscopy and density functional theory calculations. Upon applying pressure to lightly doped SnSe, we directly monitored the phase transition from semiconductor to semimetal. In addition, heavily doped SnSe exhibited a successive Lifshitz transition, activating multivalley physics. Our comprehensive study provides insight into the effects of pressure and doping on this system, leading to promising routes to tune the material properties for advanced device applications, including thermoelectrics and valleytronics.