Boron carbide doped DLC coating can combine the property superiority of these two materials to create highperformance carbon-based coating, while the final property of the composite coating is strongly dependent on the proportion of coating components. The aim of this study was to investigate the effect of boron carbide content on the mechanical and tribological properties of the magnetron sputtered B₄C/a-C coatings, as well as the relevant low friction mechanism. It was found that both the carbon matrix and introduced boron carbide were amorphous and the composite coating exhibited typical columnar structure. Appropriate doping of boron carbide significantly enhanced coating hardness, toughness as well as the adhesion strength and carrying ability, and all of them reached the optimal value when the B concentration was 2.92 at.%. It was also found that the B₄C/a-C coating with B 2.92 at.% exhibited the lowest steady friction coefficient about 0.05 and highest wear resistance at 20% RH. None of boric acid was formed on the sliding interface under the tested humidity range. Thus, the improved tribological properties were mainly attributed to the enhanced mechanical properties and friction-induced formation of an intact graphitized carbon transfer layer on the counterpart under specific humidity condition.