HVOF-processed coatings are chemically inhomogeneous and are not metallurgically bonded to the substrate. As a result, components coated with HVOF experience considerable material degradation during sliding wear. Microwave hybrid heating (MHH) is a novel surface modification technique for modifying the as-sprayed properties of the coating. Hence, this paper investigates and compares the wear and frictional behavior of HVOF as-sprayed coatings against MHH samples of WC-CrC-Ni and WC-Co/NiCrFeSiB coatings at elevated temperatures. MHH had a significant impact on wear rate and coefficient of friction by optimizing the porosity, integrated oxide phases and intersplat cohesion strength of the coatings. A modified domestic oven was used to perform MHH on HVOF-coated samples for 5 min at 1200 °C. Wear tests were performed using a pin-on-disk tribometer from room temperature to 200, 400, and 600 °C with Al2O3 disk as a counterface. SEM/EDS and XRD were utilized to examine the microstructural characterization of the coatings and substrate. Both the coatings showed higher wear resistance than the substrate at all temperatures. The WC-Co/NiCrFeSiB coating produced an oxide layer on the worn surfaces and integrated WC, CoWO4, and Fe2SiO4 splats, enhancing wear resistance. The MHH WC-CrC-Ni coating formed Cr2O3 and NiWO4 phases on the worn surfaces, increasing the intersplat cohesion strength between matrix and carbide splats, lowering the overall wear rate. After MHH, the wear rate of a substrate and WC-CrC-Ni coating was 3.5 and 1.12 times more at room temperature and 8.07 and 2.92 times more at 600 °C than WC-Co/NiCrFeSiB coating.