A Fe-Al intermetallic compound coating was prepared on AISI H13 steel by hot-dip aluminizing and subsequent high-temperature diffusion. Dry sliding wear tests of the Fe-Al intermetallic coating were performed at 298 K to 873 K (25 °C to 600 °C). The wear behavior of the Fe-Al intermetallic coating was noticed to vary markedly with the temperature and load. At 298 K (25 °C), the wear rate rapidly increased with an increase of the load. As the temperature was elevated, the wear rate dramatically decreased except for the cases under 300 N at 473 K and 673 K (200 °C and 400 °C). The Fe-Al intermetallic coating possessed an excellent elevated-temperature wear performance, especially at 673 K to 873 K (400 °C to 600 °C), but worse room-temperature one, which were noticed to be attributed to the existence and inexistence of thin tribo-oxide layers, respectively. Such a thin tribo-oxide layer was considered to provide a protection for the intermetallic compound. When the tribo-oxide layer did not form at room temperature or the formed one was massively delaminated above the critical load at elevated temperatures, Fe-Al intermetallic coating possessed poor wear resistance.