The volatilization behavior of rhenium in the process of oxidative roasting of a molybdenite concentrate with 43.55 wt.% Mo and 321 g/t Re is explored based on identifying the relationship between volatilization of sulfur and rhenium. The results show that rhenium volatizes after sulfur and precise control of operating variables plays an important role in separating rhenium from molybdenite concentrate. When the roasting parameters are optimized as follows: roasting temperature 600°C, roasting time 2 h, roasting atmosphere air, the volatilization rate of rhenium reaches 89.26%. In the process of solidification roasting, the volatilization rate of rhenium decreased almost to zero when the ratio of slaked lime/molybdenum concentrate was 10% excess to the stoichiometric requirement at 600°C for 2 h.