Abstract: Ultrafine particles prepared by evaporating pure Fe in CH4 atmosphere using arc-dischargeheating method, were found to consist of Fe-C solid solution, γ-Fe and Fe3C phases. EfFect of annealing temperature on phase transformation and hyperfine interactions has been investigated by Mossbauer spectroscopy, X-ray diffraction (XRD), differential thermal analysis and thermogravimetry (DTA-TG), transmission electron microscopy (TEM), oxygen determination and vibrating sample magnetometer (VSM) measurements. It was observed that phase transformation of γ-Fe to α-Fe occurs during annealing in vacuum. The mechanism causing the change of hyperfine interactions with annealing temperature differs for Fe-C solution and interstitial compounds. DifFerence of hyperfine interactions of Fe-C solid solution in the starting sample and its annealed samples is ascribed to the improvement of activation of interstitial carbon atoms. Stress-relieving in structure of annealed Fe3C particle can result in a weak influence on hyperfine interactions. Parameters fitted to the Mossbauer spectra show the existence of superparamagnetism in all the samples. Absorbed and combined oxygen on particle surface of the starting sample were determined.