Micro-structure on metal surface can be created with high precision and good surface quality by ultrasonic-assisted electrochemical micromachining (USEMM). One of the prevalent material removal mechanisms in ultrasonic machining (UM) is cavitation erosion. However, the mechanism of material erosion is not clear and worth investigating. This study of the mechanical and chemical effects of the ultrasonic vibration in 6061 aluminium alloy is targeted to reveal the material processing mechanism in USEMM. Based on the built model, the velocity of micro-jet produced near the workpiece surface by ultrasonic cavitation reaches up to 350 m/s when bubble collapses computed by software MATLAB. The impact of micro jet produces plastic micro-pits on the metal surface and the convex peak around the edge of the pits, which is verified in ABAQUS software. The metallographic microscope and curves of the electrochemical polarization behaviour results indicate a significant grain refinement and a marked increase of anodic dissolution current, as well as a weaker resistance than the original workpiece in NaNO3 electrolyte during UM. The current-time curve during machining demonstrates the passive layer forms on the metal surface and then breaks down at the time of less than 0.0066s in USEMM. Micrographs of scanning electron microscope (SEM) of the machined surface in different stages show that many uniform and flat pits are formed in USEMM, compared with the local uneven pits in EMM.