One of the promising methods used for the surface strengthening of metals is the electrospark alloying (ESA). Although the doping method allows one to harden quickly and easily a variety of surfaces of metals and alloys, still materials which may form optimal friction couples in friction with electrospark coatings are insufficiently investigated. Therefore, the aim of this work was to obtain coatings and determine optimal friction couples.  Samples of steel 45 were tested for friction and wear resistance with molybdenum, chromium, and stellite B3K coatings deposited applying a regular electrospark method. The samples were coated with three layers of one and the same material in the mode of 3-4-3 using an EFI-10M industrial unit. Tribological tests of the coatings were carried out in a tribological laboratory of the Aleksandras Stulginskis University (Kaunas, Lithuania) using an upgraded friction machine SMC2. All coatings were tested for friction and wear using the discs of three types (steel 45 HRC 50-52 disc, steel 30CrMnSiA HRC 38-42 and steel 30Cr13 HRC 43-45 discs) in order to determine the optimal friction and wear couples. The wear of the samples was determined by weighing on an electronic balance with an accuracy of 0.1 mg. The friction and wear tests of all coatings were performed at a load of 900 N in a gear oil 80W-90 with a 35-mm diameter disc, with a fixed rotating speed of 600 rev/min and a sliding distance up to 30,000 m. It is determined that molybdenum coatings had the highest microhardness with respect to all types of microhardness, i.e., average (8722 MPa), minimal (7468 MPa), and maximal (10849 MPa). So molybdenum coatings during work with the disks from steel 45 have formed optimal friction couples.  It is found that the wear of the 30CrMnSiA steel discs against chromium coatings was two times less than the wear of steel 45 discs. This shows that chromium coatings are more compatible with 30XGCA HRC 38-42 steel during their rubbing in oil, than with steel 45 HRC 50-52. However, even though stellite B3K coatings were worn by 43% less than during the work with steel 45 discs, they were more heavily worn out with 30CrMnSiA HRC 38-42 steel discs. However, the molybdenum coatings, when working with discs of steel 30CrMoSiA, again formed the optimal friction couple. It is proved that during the work with discs made of steel 45 HRC 50-52 and steel 30CrMnSiA HRC 38-42, the molybdenum coatings were the most suitable ones for antifriction (at the beginning, respectively f = 0.12-0.11, and at the end of tribotests f = 0.04-0.034).  It is shown that all friction couples formed of alloyed samples and the discs from steel 30Cr13 exhibited a higher wear resistance compared to that at the friction of electrospark coatings with the discs from steel 45 and steel 30CrMnSiA. The wear of all of the discs decreased substantially. Particularly, the wear of the steel 30Cr13 discs was reduced in comparison with that of the steel 30CrMnSiA discs during the work with chromium coatings more than five times, and with stellite B3K coatings - 3.3 times. It was only during the work with molybdenum coatings that the wear of the discs decreased insignificantly, only 21%. It is also noteworthy that chromium coatings displayed the highest wear resistance of all coatings explicitly during the work in couples with the steel 30Cr13 HRC43-45 discs. To sum up, in this work it was found that the most optimal friction couple of all tested ones (with electrospark coatings applied) is that consisting of the sample coated with chromium and the disc made of steel 30Cr13.  This work was supported, in part, by the institutional project of the Academy of Sciences of Moldova (Pr. No 11.817.05.05A)  and FP7 program IRSES Project ― “Oil and Sugar” (GA -2011-295202).