Tellurium is widely used in semiconductor materialsTellurium recovery, infrared detection, etc. Global more than 90% of the tellurium comes from the anode sludge produced by copper electrolytic refining, and about 30% of the tellurium in the anode sludge exists in the crude silver alloy after fire refining. There are two methods for refining crude silver: oxidative refining and electrolytic refining. Oxidative refining has a long cycle time, and it is difficult to recover the tellurium slagSlags with a large loss of silver. It is difficult to separate silver and tellurium by electrolytic refining due to the similarity of the electrode potentials of silver and tellurium. In this study, the saturated vapor pressure, separation coefficient, molecular mean free path, binary phase diagram, three-phase equilibrium diagram, and vapor–liquid equilibriumVapor-liquid equilibrium phase diagram of silver and tellurium under vacuum were calculated theoretically, and the feasibility of vacuum separation was analyzed thermodynamically. Finally, the experimental verification was carried out in the vacuum distillationVacuum distillation-gradient condensationGradient condensation experiment, the direct recovery of tellurium at 1573 K and 10 Pa was 97.93%, and the separation of silver and tellurium was achieved.