Molybdenum-doped diamond-like carbon (Mo-DLC) coatings have been deposited on titanium β-21S alloy (Ti–15Mo–3Nb–3Al–0.2Si) using plasma-enhanced chemical vapor deposition (PECVD) equipped with pulsed-DC magnetron sputtering. Mo contents in the deposited coatings have been controlled with an applied sputtering pulse duty cycle. Chemical composition, structure, morphology, and topography have been studied using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and atomic force microscopy (AFM), respectively. XRD pattern of the coating with highest Mo content shows the presence of carbide phase. Smooth features with low roughness values are observed in low Mo content coating, whereas high Mo content coating shows granular characteristics with a high roughness value. Raman spectra reveal the increased graphitic content for the highest metal concentration in the coatings, wherein the nanohardness is also determined to be highest, at about ~18–19 GPa. Furthermore, the ball-on-disk tribometry test on Mo-DLC coating with highest nanohardness shows a low coefficient of friction (COF) of 0.2 with low wear loss compared to that of the substrate (0.62).