Ti6Al4V alloy manufactured by electron powder bed fusion (EPBF) was separately heat-treated by stress-relief annealing at 600 °C, annealing at 800 °C, and solid solution at 920 °C for 1 h. Then, the friction and wear tests were conducted on the samples before and after heat treatment to analyze the properties and mechanism of friction and wear behavior. Results show that the sample annealed at 600 °C for 1 h has the optimal wear resistance, and the wear mass loss reduces by 44%. The sample annealed at 800 °C for 1 h possesses the optimal anti-friction performance, and the coefficient of friction reduces by 14%. This research provides a simple heat treatment method to improve the friction and wear resistance of Ti6Al4V alloy manufactured by EPBF.