This work presents the results of tribological tests of Mo and combined coatings TiAlC formed using electrospark alloying (ESA) technology and additionally processed using thermochemical electrolyte anodic heating (TEAH). ESA makes it possible to form 15–20 µm thick coatings on the friction surface, characterized by a high hardness and wear resistance. Tribological studies were performed by testing the block-on-roll friction pair under 300 N and 600 N loads. The duration of the tests was 180 km of friction path, and the constant rotation rate of the disk was 600 rpm. It was observed that the friction torque during the 300 N loading tests was stable for all samples and throughout the entire testing period, whereas at 600 N loading, the pair with the Mo coating had a decreasing trend, and the pair with the TiAlC coating, friction torque slightly increased. For a reference sample without the coating trend of friction torque became drastically unstable. At both loads (300 N and 600 N), the friction pair with the reference sample had the highest cumulative wear, and the pair with the Mo coating had the lowest. At both loads, the cumulative wear of the friction pair with Mo coating is about 2 times lower than the TiAlC, and ≥1.8 times lower than the control (not coated) version. This study shows that at lower loads, the friction pair formed by the TiAlC coating and steel C45 is more matched than the friction pair with Mo coating.