We investigate the thermal stability of Mo/SiC multilayer coatings at elevated temperatures. Transmission electron microscopy and x-ray diffraction studies show that, upon annealing, a thermally induced structural relaxation occurs that transforms the polycrystalline Mo and amorphous SiC layers in as-deposited multilayers into an amorphous Mo-Si-C alloy and crystalline SiC, respectively. After this relaxation process is complete, the multilayer is stable at temperatures up to 400 degrees C.