With the increasing demand for the high agility and fast response of high-level equipment in the aerospace and energy power fields, it is increasingly urgent to improve the performance of the high-temperature and wear resistance of the corresponding high-level components. Ceramic-reinforced titanium matrix composites have excellent high-temperature and wear resistance, but, in laser additive manufacturing, the primary ceramic phase is coarse, and the morphology of the ceramic phase is difficult to control, which limits their further development. In this investigation, a follow-up ultrasonic-assisted laser-additive-manufacturing method was proposed to prepare a 30 wt.% TiC/Ti6Al4V composite coating on a Ti6Al4V surface. Under the effects of ultrasonic cavitation and acoustic streaming, the content of the unmelted TiC was reduced, the dendritic primary TiC in the solidification process was broken and the distribution uniformity of the primary TiC was improved. The content of the unmelted TiC in the composite coating decreased significantly under ultrasonic action, and it was only 50.23% of that without ultrasonic action. At the same time, the average size of the dendritic primary TiC in the composite coating decreased from 61.59 μm to 27.04 μm, which was 56.10% smaller than that without ultrasonic action. The average microhardness of the composite coating reached the maximum of 656.70 HV0.2 under ultrasonic power, and it was 83.21% higher than that of the Ti6Al4V substrate, and 26.44% higher than that of the composite coating without ultrasonic power. Due to the ultrasonic-cavitation and acoustic-streaming effects, the content of the unmelted TiC obviously decreased, so that the average friction coefficient of the composite coating increased, and the wear mechanism changed from abrasive wear to adhesive wear.