Stellite 6 coating is cladded on the stainless steel using a fiber laser. The effect of heat treatment on the microstructure of the coating is investigated at various temperatures. Further, a tribometer with a pin-on-disk configuration at high temperatures (600 ℃, 700 ℃, 800 ℃, and 900 ℃) is used to evaluate the sliding wear behavior of the coating during interaction with alumina for identifying the applicable working temperature range of the coating. The results denote that the coating predominantly comprises carbide eutectics and a Co-rich solid solution exhibiting fcc and hcp structures. The microstructure of the coating is thermally stable at 700 ℃. However, the eutectics are critically decomposed with the secondary precipitation of fine particles after heat treatments at 800 ℃ and 900 ℃. The transformation temperature from fcc to hcp structures of Co-rich solid solution is 700-800 ℃. In case of the Stellite 6 coating, wear at high temperature can be observed during the initial stage of the friction process. The wear loss drastically decreases once the glaze layer is formed. Among the friction temperatures, the wear loss at 700 ℃ is observed to be the lowest. Ploughing and adhesion are the wear mechanisms at 600 ℃. Slight glaze layer is formed on the surface of the coating, which is loosely bound with the coating. At 700 ℃ and 800 ℃, the coating exhibits abrasion and adhesion, and compact glaze layer is formed and bound tightly with the coating. At 900 ℃, the coating is considerably softened, leading to tough plastic deformation during the initial stage of the friction process. Therefore, the applicable working temperature range of the laser-cladding Stellite 6 coating is 700-800 ℃.