Iron-carbon and Iron-carbon-silicon white cast iron rods were sprayed by use of a thermal spraying gun and the characteristics of the very rapidly solidified coatings were investigated by means of X-ray diffraction and micro-hardness test. Coatings about 0.1mm in thickness consisted of austenite and close-packed hexagonal ε-iron. The ε-iron phase decomposed to ε-carbide and martensite at temperatures lower than 200°C and the austenite phase broke up at temperatures lower than 400°C. X-ray diffraction profile of the coatings about 0.4mm thick revealed a very broad peak around (011) α through low temperature tempering during thermal spraying. The hardness of the coatings came to the maximum between 100°C and 400°C due to precipitation of fine ε-carbide or cementite and decreased gradually with an increase of tempering temperature over 400°C because of coarsening of carbide particles.