A new technology of treating molybdenum residues by simultaneous ultrafine milling and alkali leaching was put forward to recover molybdenum from metallurgical residues. The effects of residue size, milling time, solid content,n(Na₂CO₃)/n(Mo) and slurry pH value on molybdenum leaching rate were investigated. The results indicate that a simpler process, lower slurry temperature, 50% shorter treating time, 60% decrease of Na₂CO₃content and 15% increase of molybdenum leaching rate can be obtained by the new technology compared with the traditional process. The leaching kinetic equation was determined, and calculation of active energy (E=56.2 kJ/mol) shows that the leaching process of molybdenum residues by simultaneous ultrafine milling and alkali leaching is controlled by chemical reaction. Potential exists for the new process to form the basis for an economically viable, environmentally friendly process to recover valuable elements from residues.