The study of the leaching of vanadium (V) and molybdenum (Mo) from spent petrochemical catalysts in sodium hydroxide (NaOH) medium was performed using two approaches, namely, conventional leaching and microwave-assisted leaching methods. The influence of microwave power, leaching time, leaching temperature, and NaOH concentration on the leaching efficiency of spent petrochemical catalyst was investigated. Under microwave-assisted conditions (600 W, 10 min, 90°C, 2.0 mol·L？1 NaOH, and 0.20 g·mL？1 solid-liquid ratio), the leaching efficiencies of V and Mo reached 94.35% and 96.23%, respectively. It has been confirmed that microwave energy has considerable potential to enhance the efficiency of the leaching process and reduce the leaching time. It is suggested that the enhancement of the leaching efficiencies of V and Mo can be attributed to the existence of a thermal gradient between solid and liquid and the generation of cracks on the mineral surface.