The leaching mechanism of gallium (Ga) and germanium (Ge) from zinc powder replacement residue (ZPRR) was investigated through ultrasonic-assisted sulfuric acid leaching. Characterization via XRD, SEM, XPS, and FT-IR revealed that ultrasonic treatment promotes the dehydration of H₄SiO₄ colloids, thereby reducing their adsorption capacities for Ga and Ge complexes. Additionally, ultrasound enhances the dissolution of CaS in H₂SO₄, increasing H₂S production, which aids in the reduction of Fe³⁺ and mitigates iron precipitate formation. Process parameters including ultrasonic power (0−450 W), temperature (100−120 °C), and leaching time (30−120 min) were systematically optimized, achieving optimal leaching efficiencies of Ga and Ge at 95.7% and 94.5%, respectively.