A multiphasic composite coating on steel was fabricated by reaction synthesis in the melt. The ceramic particulate reinforced intermetallic matrix composite (TiC p/Ni 3Al) and the mixture (TiC p/Ni 3Al-Fe) of the composite and steel were successively formed from the coating surface to the steel matrix. Metallurgical fusion of the reactive products with the steel melt occurred to form the multiphasic composite coating after solidification. The Ti-C-3Ni-Al system was employed to synthesize the composite coating. The reaction processes of the system were investigated using a differential scanning calorimeter and an X-ray diffractometer. The coating presented higher elevated-temperature wear resistance than H13 steel and markedly postponed the transition from mild wear to severe wear.