TiNi/Ti2Ni alloyed layer was prepared on surface of Ti6Al4V alloy by plasma surface alloying process. Surface morphology, composition distribution, cross-section morphology and phase structure of Ni modified layer were analyzed. Sliding dry friction performance of TiNi/Ti2Ni alloyed layer was observed and analyzed under different loads by Pin-on-disc test, and compared with the TC4 substrate. The results indicate that the wear mechanism of both TiNi/Ti2Ni alloyed layer and the TC4 substrate shows abrasion wear. Under the same wear condition, the friction coefficient of TiNi/Ti2Ni alloyed layer is slightly lower than that of the TC4 substrate, the wear resistance of TiNi/Ti2Ni alloyed layer is better than that of TC4 substrate. Friction coefficients under different loads fluctuate between 0.29~0.33 and wear rate increases with increasing of load.