Strengthening titanium alloys and mitigating their wear degradation at various temperatures is the key to industrial applications. In this study, high-performance Ti6Al4V alloy (here, Ti with 6.25 wt% Al and 4.17 wt% V) was prepared by laser solid forming (LSF). The phase and microstructure of the Ti6Al4V alloys were systematically examined, and the overall improved mechanical properties were achieved. The coefficient of friction (CoF) and wear of LSFed Ti6Al4V alloy against WC-6%Co cemented carbide using a ball-on-disc tribometer at various temperatures revealed a temperature-dependent wear mechanism. During the experiment, the CoF of LSFed Ti6Al4V would increase initially and then decrease with the increased temperature. This trend is determined by the abrasive wear dominating at a lower temperature, and it gradually changes to oxidative wear and fatigue wear under higher temperatures. LSF provides a promising way to achieve supreme mechanical and tribological properties in Ti6Al4V simultaneously.