Tungsten carbide-12 wt.% cobalt coatings were deposited using optimized high-energy plasma (HEP) and high-velocity oxygen fuel (HVOF) thermal spray techniques. The coatings were evaluated using transmission electron microscopy, differential thermal analysis, X-ray diffraction, and subjected to wear tests to relate the coating structure to wear performance. Coatings were evaluated in the assprayed condition, as well as after heat treatments in inert atmosphere. The results indicate that a substantial amount of amorphous matrix material is created during the thermal spray process. Carbon and tungsten, liberated through the dissociation of the WC, combine with cobalt present in the starting powder to form amorphous material on solidification. Differential thermal analysis revealed an exothermic reaction for both the HVOF and HEP coatings at approximately 853 and 860 °C, respectively, which did not occur for the powder. Post-coating heat treatment in an inert atmosphere resulted in the recrystallization of the amorphous material into Co6W6C and Co2W4C, which was dependent on the time and temperature of the heat treatment. Wear testing showed improvement in the wear performance for coatings that were subjected to the heat treatment. This was related to the recrystallization of the amorphous matrix into eta phase carbides.