The novel process known as ultrasonic-assisted laser shock peening (ULSP) is conducted on hot rolled Ti6Al4V titanium alloy with polished surface to improve its cavitation erosion (CE) resistance. The microstructure and phase structure were investigated by transmission electron microscope and X-Ray diffractometer. The microhardness and residual stress were measured by microhardness tester and X-Ray residual stress analyzer. After that, the CE mass loss and morphology were analyzed through high-precision analytical balance and scanning electron microscope to reveal the CE resistance mechanism of ULSP. The results show that ULSP treatment causes plastic deformation at the surface layer, resulting in refined grains and complex dislocation structures. The aforementioned process produces a hardened layer and compressive residual stress (CRS) layer with notable amplitude and deep influence. The surface microhardness of the ULSP-9J specimen is 410 ± 4 HV, which is a 14.8 % increase compared to the LSP-9J specimen. The CRS of the ULSP-9J specimen is −329 ± 6 MPa. As a result, it is vital in preventing the formation and propagation of CE cracks, strengthening the material's resistance to CE damage, reducing mass loss, and enhancing the overall morphology of CE.