Extraction and recovery of W and Mo from waste scraps hold significant importance for sustainable resource utilization and environmental protection. Ultrasonic-assisted leaching was demonstrated to be a clean and efficient method for metal dissolution and separation, and the research emphasis of this work was focused on ultrasonic electrochemical behaviors. The HNO3 leaching behaviors of W and Mo under conventional and ultrasonic-assisted processes from powdery W-Mo mixture scraps generated in the powder metallurgy process were investigated. It’s demonstrated that Mo and W can be selectively separated by the regulation of lixiviant concentration and temperature, in which the Mo is converted into the soluble ions (MoO22+) while the W particle is kept in original metallic state and covered with insoluble WO3·H2O. Experiment results indicated that 96.38 % Mo and 8.03 % W were rapidly leached in 2 mol/L HNO3 within ultrasonic-assisted leaching for 10 min at 25 °C, showing a favorable pre-separation effect. Phase transformation and microstructure evolution of the leaching residues under conventional and ultrasonic-assisted leaching processes were analyzed. It’s suggested that Mo can precipitate in the form of molybdenum oxide hydrates, covering the unreacted particle surfaces and further hindering the Mo leaching, especially at higher temperature. This unfavorable situation can be relieved by the introduction of ultrasonic cavitation effect. Importantly, the electrochemical dissolution behaviors of pure W, pure Mo, and W-Mo alloy sheets in HNO3 solution were compared employing the potentiodynamic polarization and electrochemical impedance spectroscopy testing to reveal the ultrasonic intensifying mechanism in this study. Eventually, the ultrasonic electrochemical intensifying mechanism can be referential for the efficient dissolution of metal-based scraps for resource recycling.