Pure Fe-3.5wt% C alloy was surface melted using a cw CO2 laser and the microstructure of the laser tracks was investigated by scanning and transmission electron microscopy. Structure of the melted zones consisted of dendrites of partially transformed primary austenite and of very fine lamellar ledeburite. The secondary dendrite arm spacings were indicative of a cooling rate of similar to 10(5) K s(-1), in good accord with calculations based on the model of a moving Gaussian beam. Using methods of quantitative metallography the volume fraction of dendrites within the melted zone and the volume fractions of the carbide and ferrite phases in the decomposed ledeburite were estimated. These data were combined with the results of a quantitative X-ray diffraction phase analysis (see Part II) and compared with the equilibrium phase diagram. It was found that the volume fraction of dendrites was near the equilibrium value while the volume content of cementite in the rapidly solidified structures was considerably higher than predicted from the equilibrium phase diagram.