The effects of microwave roasting on separation of rhenium (Re) and molybdenum (Mo) from a molybdenite concentrate have been investigated based on evaluation of the heating characteristics of the concentrate in the microwave field. The results show that a variety of operating variables, namely microwave power, sample weight, sample geometry, roasting temperature, roasting time and atmosphere significantly impact on the volatilization rates of Re and Mo. The optimum conditions for Re-Mo separation are microwave power 1300 W, sample weight 20 g, sample geometry pellets, temperature 600 °C, time 1.5 h, and atmosphere 20%O₂. Under these experimental conditions, the volatilization rate of Re reaches 88.12%, while that of Mo is just 5.15%. Microwave-assisted roasting provides an alternative route to separating Re and Mo from molybdenite concentrate.