A novel ultrasonic vibration assisted (UVA) wire arc additive manufacturing (WAAM) was used to fabricate Cu-8Al-2Ni-2Fe-2Mn alloy in this study. The effect of different interpass temperatures with and without ultrasonic vibration on the microstructural evolution and mechanical properties of the fabricated part were investigated by optical microscope (OM), scanning electron microscope (SEM), transmission electron microscope (TEM), nanoindentation, and mechanical tensile testing. The results showed that reduction of the interpass temperature without UVA treatment cannot prevent the columnar dendrites directionally growing along the deposition direction. Under the UVA treatment, the coarse columnar dendrites were broken at the interpass temperature of 400 °C, and formed a fine cellular structure with an interpass temperature of 100 °C, owing to the acoustic streaming effect and cavitation effect. In addition, globular κII phase was based on Fe3Al and lamellar κIII phase was based on NiAl distributed in the interdendritic region, whereas κIV phase (rich-Fe) were precipitated in the α-Cu matrix. The improvement of microstructural characteristics caused by UVA treatment further improved the tensile properties and nano-hardness of WAAM fabricated parts. Eventually, it is experimentally demonstrated that WAAM fabricated Cu-8Al-2Ni-2Mn-2Fe alloy can obtain high-performance at UVA process under an interpass temperature of 100 °C.