Abstract Classical molecular dynamics (MD) simulations are conducted to examine the atomic-scale friction behavior of an infinite flat–flat contact between copper(0 0 1) and diamond(1 1 1) surfaces. Two types of diamond surface, namely H-free and hydrogenated, are constructed and on each of them the copper counterface is brought to slide along the [1 1 −2] and [1 −1 0] crystallographic directions with a variety of loads. The simulation results demonstrate that the hydrogen atoms chemisorbed to the diamond surface can to large extent eliminate the directional dependency of its friction behavior with copper. Under pressures less than 30 GPa, the sliding between copper and hydrogenated is wearless. In this period, the shear stress of them just slightly increases to 0.6 GPa. Between 30 GPa and 32 GPa, copper atoms near the interface begin to be worn and incorporate into the diamond substrate and this causes a sharp shift from 0.6 GPa to 2.7 GPa in their shear stress. In contrast, the sliding process between copper and H-free diamond is always wearless even under pressure beyond 40 GPa. The H-free [1 −1 0] model exhibits much higher shear stress than H-free [1 1 −2] under pressures less than 35 GPa. Beyond 35 GPa, they present nearly consistent shear stress evolution. Moreover, the simulations for hydrogenated diamond models suggest that their friction behavior is independent on sliding velocity only under wearless sliding regime.