Boron doping of diamond-like carbon coatings has multiple effects on their tribological properties. While boron typically reduces wear in cutting applications, some B-doped coatings show poor tribological performance compared with undoped films. This is the case of the tribological tests presented in this work in which an alumina ball is placed in frictional contact with different undoped and B-doped amorphous carbon coatings in humid air. With B-doped coatings, a higher friction coefficient at a steady state with respect to their undoped counterparts was observed. Estimates of the average contact shear stress based on experimental friction coefficients, surface topographies, and Persson's contact theory suggest that the increased friction is compatible with the formation of a sparse network of interfacial ether bonds leading to a mild cold-welding friction regime, as documented in the literature. Tight binding and density functional theory simulations were performed to investigate the chemical effect of B-doping on the interfacial properties of the carbon coatings. The results reveal that OH groups that normally passivate carbon surfaces in humid environments can be activated by boron and form B-O dative bonds across the tribological interfaces, leading to a mild cold-welding friction regime. Simulations performed on different tribological pairs suggest that this mechanism could be valid for B-doped carbon surfaces in contact with a variety of materials. In general, this study highlights the impact that subtle modifications in surface and interface chemistry caused by the presence of impurities can have on macroscopic properties, such as friction and wear.