Titanium alloy has extensive applications in numerous fields, such as in aerospace, shipbuilding, petrochemical, and bio-medical. However, under the condition of high temperature (above 700 °C), it is difficult to meet the requirements of the performance of the turbine blades, piston rings, valves, etc. In this paper, the alloy powder is composed of Ni60A, TiN, Al, and Si in accordance with the proportion of 1:3:4:2 (mass ratio), and the composite coating, such as TiN, TiB, Ti5Si3, and Al3Ti were synthesized on Ti-6Al-4V alloy by Yttrium Aluminium Garnet(YAG) laser. The friction and wear experiments were carried out on Ti-6Al-4V alloy and alloyed coatings at different loads (3N, 6N, 9N), and different temperatures (25 °C, 350 °C, 700 °C). The impact of load and temperature on wear performance were analyzed by analyzing the friction traces. The results showed that the abrasion loss, wear width, and depth, wear volume, and wear ratio of the alloyed coatings were less than Ti-6Al-4V alloy, and the surface of furrow was shallow and the wear was less. However, under high temperature conditions, the alloy coating wears worse than Ti-6Al-4V alloy, and the high temperature wear resistance is not ideal.