Noble lead, which is produced by the reduction smelting of lead anode slime, contains copious rare and precious metals. The vacuum distillation procedure for processing noble lead exhibits the advantages of efficiency and simplicity, and has been industrialized in most of China’s lead, copper and precious metal smelting enterprises. However, the condensation behaviors of volatile components in noble lead remain unknown, making effective Pb and Sb removal difficult; thus, the corresponding system equipment fails to meet the production requirements of separating alloys and enriching precious metals. In this paper, the condensation area of volatile components in noble lead is predicted by the molecular mean free path. Then, preliminary verification and experimental research were carried out on the condensation rules of each component to verify and revise the theory. The experimental results indicate that the dominant condensation zones of Pb and Sb are 24–44 mm and 44–59 mm, respectively. Further experimental studies show that Pb and Bi are removed to below 0.8%, and the direct yields of Pb, Bi and Ag reached 91%, 95% and 94%, respectively, with temperature of 1250 °C, holding time for 3 h and pressure of 5 Pa. This research solves the problem of difficult Pb and Sb removal in the conventional vacuum distillation process of noble lead and realizes the efficient recovery of metals, which has practical guiding significance for the technological conditions in the industrial application of this process and the equipment design. This work meets modern cleanliness, efficiency, and simple metallurgical requirements.