Carbon nitride (CNX) films (with N/C ratio of 0.5) were deposited on both untreated and plasma nitrided Ti-6Al-4V substrates by D.C. magnetron sputtering using a graphite target in nitrogen plasma. TEM and XPS analysis revealed the formation of both amorphous CNX structure and crystalline β-C3N4 phases in the deposited coatings. Nano-indentation tests showed that the film hardness was about 18.36 GPa. Both the scratch tests and indentation tests showed that compared with CNX film deposited directly on Ti-6Al-4V, the load bearing capacity of CNX film deposited on plasma nitrided Ti-6Al-4V was improved dramatically. Ball-on-disk wear tests under both dry sliding and lubricated conditions (with simulated body fluids) were performed to evaluate the friction and wear characteristics of the deposited coatings. Results showed that under both dry and lubricated conditions, the duplex treated system (i.e., with CNX film deposited on plasma nitrided Ti-6Al-4V substrate) was more effective in maintaining a favorable low and stable coefficient of friction and improving wear resistance than both individual plasma nitriding and CNX films on Ti-6Al-4V substrate. Under dry sliding conditions, the generated wear debris of spalled films were accumulated on the wear track, mechanically alloyed and graphitized, thus significantly reducing the coefficient of friction and preventing wear of the substrate. However, under lubricated conditions, due to the flowing of the fluids, the lubricating wear debris was taken away by the fluids, and therefore, the direct contact of two original surfaces resulted in high coefficient of friction and extensive abrasive wear of the substrate for CNX films deposited on Ti-6Al-4V substrate. Also when there was some small-area spallation of CNX films, the fluids could seep into the interface between the film and substrate, thus degrading the interfacial adhesion and resulting in a large area spallation.