The carburized layer with special physical and chemical properties was prepared on the surface of titanium alloy Ti6Al4V making use of double glow discharge plasma carburizing technique and hollow cathode effect, with a netlike highly pure graphite as the source cathode, titanium alloy as the cathode, and Ar as the working gas. The phase compositions and C distribution of the carburized layer were determined by means of X-ray diffraction and glow discharge spectrometry. The friction and wear behavior of the carburized Ti6Al4V alloy specimen sliding against GCr15 steel was evaluated on a BDW-2 ball-on-disc test rig. The microhardness of the carburized layer was measured, the elemental composition of the carburized layer determined by means of energy dispersive spectrometry, and the metallorgraphic structure and worn surface morphologies of the carburized specimen were observed on an optical microscope. It was found that hard phase TiC was formed in the carburized layer, which contributed to increasing the hardness and wear resistance of the carburized surface. The improvement in the friction and wear behavior of the carburized specimen was attributed to the changes in the composition, structure, and hardness by the carburizing.