Molybdenite concentrates are usually treated by roasting, but low concentration SO2 pollution is a problem. Extraction of molybdenum and rhenium from molybdenite concentrates with a pressure oxidative leaching (POX) and solvent extraction (SX) process was studied. A series of POX-SX laboratory and pilot tests were carried out on the molybdenite concentrate. In the POX stage, more than 95% rhenium and 15-20% molybdenum were leached into solution. Solvent extraction recovered the rhenium and molybdenum from the POX solution. The extraction rates of Re and Mo were above 98%. The loaded organic reagent is stripped with ammonia. The stripping ratio of Mo is more than 98%. Compared to the roasting process, the total recovery of Mo increased from 93% to 97%, and Re from 60% to 90%. In the coming five years, POX-SX technology will be competitive in China.