The present study aimed to investigate the tribological behavior of high-temperature vacuum-brazed WC-Co-NiP functional coatings deposited on 16MnCr5 case hardening steel. Dry sliding wear resistance was evaluated using a non-conformal ball-on-disk arrangement, at room temperature against 100Cr6 and WC-Co static partners, respectively. Morphological, microstructural, and chemical composition analyses showed a complex, phased structure composed of tungsten carbide, nickel, and hard cobalt-based η-structure. In the testing conditions, the coefficient of friction against 100Cr6 and WC-Co counterparts entered a steady-state value after approximately 1000 m and 400 m, respectively. The wear track analysis revealed phenomena of particles trapped between the sliding bodies, as well as gradual removal of asperities. The calculations of the wear rates proved that the values were strongly influenced by properties of the sliding system, such as crystal structure, stress discontinuities, hardness, and material homogeneity.