Single particle experiments were carried out in the present study. An industrial copper matte powder, containing 68.04 wt.% Cu, 0.50 wt.% Se and 0.08 wt.% Te was taken as the starting material. Se and Te phase assemblies and distribution behaviors were systematically investigated in the air atmosphere. It was found that Se reported to blister copper, matte, and oxide phase, whilst Te will enrich in oxide phases, including phases in the Fe-Si-Te-O, Ca-Fe-Te-O, and Ca-Te-O-(S) systems. As the temperature increases, the selenium and tellurium content in the copper and matte phases decreases. The introduction of CaO flux, and typical impurities of Pb and Si, had significant influence on Se and Te distribution. The results revealed that CaO addition and Si impurity accelerated the removal of Se and Te from the copper and matte phases, but Pb impurity increased Se and Te in Cu-rich phases.