The results of studies on the distribution of rare elements among the products of distillation processing of polymetallic mattes are present in this article. Schemes of the developed technological equipment for the implementation of the extraction processes of rare elements via the vacuum distillation of mattes are presented. Technological tests were performed with a matte of lead, copper, and antimony plants at 1100–1250 °C and a pressure of up to 700 Pa. It was established that As, Cd, Bi, In, and Ge, by more than 90% in total, are extracted into condensate and dust in the distillation process of volatile components from mattes of lead production. At the same time, antimony is distributed between the distillate residue and condensate. Antimony by 90.47%, arsenic by 78.83% and cadmium by 98.72% are distributed into sulfide condensate and dust in the distillation of copper production matte. From the matte of the antimony plant, Sb and Bi (90.76% and 89.78%, respectively) are transferred into the condensate and cyclone dust. Arsenic is distributed between the liquid and vapor phases. Based on calculations, Se and Te will be mainly concentrated in the distillation residue. High-grade copper mattes obtained in processing mattes from lead and copper plants can be further used to obtain metallic copper by converting. The condensate and dust can be processed separately or with the dust of the mainline production for rare metal extraction. Antimony matte processing condensate containing more than 70% Sb can be directed to the process of crude antimony refining.