Due to lack of proper treatment methods, Pb pollution caused by improper treatment of electronic wastes (e-waste) has been attracting increasing attention. This paper investigates the separation behavior of Pb in the presence of Cu and other metallic particles (Cd, Bi, and Zn), in order to separate and recover various metals effectively from the copper-rich particles of crushed e-wastes. Vacuum metallurgy separation method is adopted to separate and recover Pb from the copper-rich particles of crushed e-wastes. Due to the variety and complexity of metals in copper-rich particles, this paper studies the effects of Cu, Cd, Bi, and Zn on vacuum separating and recycling of Pb. It is found that Cu particles have both a positive dispersing and a negative blocking effect on Pb evaporation. Cd can be evaporated preferentially, and then Pb can be subsequently separated for their huge vapor pressure gap. The formation of Pb-Bi alloy with a low vapor pressure makes the separation of Pb more difficult. As a result of different condensation characteristics, Pb and Zn can be evaporated together from Cu particles, and then be respectively condensed on different positions as pure Pb and Zn.