Tribology involves not only two-body contacts of two solid materials—a substrate and a counter-surface; it often involves three-body contacts whether the third body is intentionally introduced or inevitably added during the sliding or rubbing. The intentionally added third body could be lubricant oil or engineered nanomaterial used to mitigate the friction and wear of the sliding contact. The inevitably added third body could be wear debris created from the substrate or the counter surface during sliding. Even in the absence of any solid third-body between the sliding surfaces, molecular adsorption of water or organic vapors from the surrounding environment can dramatically alter the friction and wear behavior of solid surfaces tested in the absence of lubricant oils. This review article covers the last case: the effects of molecular adsorption on sliding solid surfaces both inevitably occurring due to the ambient test and intentionally introduced as a solution for engineering problems. We will review how adsorbed molecules can change the course of wear and friction, as well as the mechanical and chemical behavior, of a wide range of materials under sliding conditions.