New experimental results have been obtained on the behavior of arsenic and other associated metals (Re and others) under conditions of oxidative and reductive sintering. It has been established that the extraction of arsenic strongly depends on the process temperature during oxidative sintering. The extraction of arsenic into dust media at 873 K is 50% and rhenium is 88–90%. The effect of excess air on the extraction of arsenic and rhenium into dust was studied: the higher the excess air coefficient, the more complete the extraction of arsenic and rhenium into the dust. The obtained data indicate that achieving a high level of arsenic extraction from the initial product is not possible during oxidative sintering. The best arsenic removal results were reached under the conditions of reductive sintering of initial material by natural gas. The extraction of arsenic into dust at 823 K was 88%, and at 1373 K arsenic is almost completely converted into dust. Obtained new experimental results have a fundamental importance for the selection and organization of a comprehensive technology for the processing complex in composition refractory gold-copper-arsenic-bearing products.