This paper discusses the topical issue of the general compatibility of tribological pairs from the point of view of wear resistance when using various electrospark coatings. For investigation, steel segments were coated with bronze, Mo, and combined Ti + Al + C coatings by electrospark treatment. Coated segments and uncoated control segments were studied in a friction pair with an unhardened C45 steel roller (15HRC) at loads of 300 and 600 N in a lubricant medium. Throughout the test, the coefficient of friction was measured, the wear rate of the tested tribo-pairs was estimated, and the nature of the wear of the friction surfaces after testing was analyzed using optical and scanning electron microscopy (SEM). The results have shown that the most compatible tribo-pairs were steel 45/Bronze and steel 45/Mo, since they have exhibited the best resistance, i.e., the least wear under both loads tested.