Abstract Selenium can be used in various applications e.g. in glass and pigment industry, electronic applications, metallurgy as a steel refining and spheroidizing element in the course of steel and non-ferrous alloys casting, agriculture and biology, space investigation, military applications, rubber industry, cosmetics, etc. and therefore the unceasing attention is paid to its recovery. Nearly whole world selenium production comes from utilization of a by-product of copper production, where it accumulates into the anodic slimes. The overview of selenium forms in anodic slimes as well as physical and chemical possibilities of its recovery is given in this paper. The attention is focused on pyrometallurgical, hydrometallurgical and combined methods of its recovery as well as on the possibility of its refining. Besides the heavy metals, the precious metals are contained in the anodic slimes. It is their high market price that stimulates the processing of anodic slime with recovery all valuable metals. From the environmental point of view, the special attention should be paid to the wasteless technologies.