In this paper, we present the results of an experimental study on WC/C coatings, deposited by using plasma-enhanced chemical vapor deposition in an N2-SiH4 atmosphere, annealed at temperatures of 200, 500 and 800 °C, in which the hexacarbonyl of W was used as a precursor. During the experiments, the topography, chemical composition, morphology, as well as selected mechanical properties, such as hardness, Young’s modulus, and coefficient of friction of the WC/C coatings were analyzed. Annealing without the protective atmosphere in the mentioned temperatures caused a decrease in hardness (up to 15 ± 2.7 GPa). In addition, the coefficient of friction value increased only to 0.37 ± 0.03.