Adhesive wear is a characteristic but inadequately studied type of wear of polymer materials. In local regions of real contact an intensive molecular (adhesive) interaction is observed under rubbing conditions, which is stronger than the bonds between individual elements in the supermolecular formations or in polymer molecules, leading to cohesive failure of the material. Wear products can escape from the contact region as gases or as solid substances, or they can form a “third body”, i.e., a transferred layer of one material is deposited on the surface of the other. The direction, mechanism, and character of the occurring processes are determined, first of all, by the structures of the interacting materials. To know the mechanism of adhesive wear enables one to predict dangerous failures of the surfaces under rubbing due to seizure, on the one hand, and to find ways of governing the frictional interaction and create efficient self-lubricated polymer-based materials on the other hand. One of the efficient ways of providing minimum wear in metal-polymer friction pairs is to govern the process of developing “friction polymers” and to use mixtures of polymers having different thermophysical properties as antifrictional materials.