Tetrahedral amorphous carbon coatings have the potential to significantly reduce friction and wear between sliding components. Here, we provide atomistic insights into the evolution of the sliding interface between naked and hydrogen-passivated ta-C sliding partners under dry and lubricated conditions. Using reactive classical atomistic simulations we show that sliding induces a sp³ to sp² rehybridization and that the shear resistance is reduced by hydrogen-passivation and hexadecane-lubrication—despite our finding that nanoscale hexadecane layers are not always able to separate and protect ta-C counter surfaces during sliding. As asperities deform, carbon atoms within the hexadecane lubricant bind to the ta-C sliding partners resulting in degradation of the hexadecane molecules and in increased material intermixing at the sliding interface. Hydrogen atoms from the passivation layer and from the hexadecane chains continue to be mixed within a sp² rich sliding interface eventually generating a tribo-layer that resembles an a-C:H type of material. Upon separation of the sliding partners, the tribo-couple splits within the newly formed sp² rich a-C:H mixed layer with significant material transfer across the sliding partners. This leaves behind a-C:H coated ta-C surfaces with dangling C bonds, linear C chains and hydrocarbon fragments.