In recent years, the effects of chromium on the transformation characteristics of pure iron and the structures produced thereby have been extensively studied as a function of cooling rate. In this paper, we present TEM observations made on specimens of Fe-10% Cr and Fe-20% Cr alloys produced through laser surface alloying process with an estimated cooling rate of 8.8 x 104°C/sec. These two chromium levels were selected in order to study their phase transformation characteristics which are dissimilar in the two cases as predicted by the constitution diagram. Pure iron (C<0.01%, Si<0.01%, Mn<0.01%, S=0.003%, P=0.008%) was electrodeposited with chromium to the thicknesses of 40 and 70μm and then vacuum degassed at 400°F to remove the hydrogen formed during electroplating. Laser surface alloying of chromium into the iron substrate was then performed employing a continuous wave CO2 laser operated at an incident power of 1200 watts. The laser beam, defocussed to a spot diameter of 0.25mm, scanned the material surface at a rate of 30mm/sec, (70 ipm).