Mechanical, structural, chemical bonding (sp3/sp2), and tribological properties of films deposited by pulsed-DC sputtering of Ti targets in Ar/C2H2 plasma were studied as a function of the substrate bias voltage, Ti-target current, C2H2 flow rate and pulse frequency by nanoindentation, Raman spectroscopy and ball-on-disc tribometry. The new findings in this study comprise: dense, column-free, smooth, and ultra-low friction TiC/a-C:H films are obtained at a lower substrate bias voltage by pulsed-DC sputtering at 200 and 350 kHz frequency. The change in chemical and phase composition influences the tribological performance where the TiC/a-C:H films perform better than the pure a-C:H films. In the case of TiC/a-C:H nanocomposite films, a higher sp2 content and the presence of TiC nanocrystallites at the sliding surface promote formation of a transfer layer and yield lower friction. In the case of a-C:H films, a higher sp3 content and higher stress promote formation of hard wear debris during sliding, which cause abrasive wear of the ball counterpart and yield higher friction.