In this work we present the study of hematite (α-Fe2O3) nanostructures synthesized by the ball milling technique. The structural characterization and the crystallite size estimation have been carried out using the X-ray diffraction (XRD) technique. Data analyses indicate that the hematite phase (space group, R-3C) is preserved after the milling process. As the milling time is increased, a second phase (α-Fe) appears. The mean crystallite size shows a decreasing tendency as the milling time is increased. High-resolution transmission electron microscopy (HRTEM) images show the formation of grains composed of crystallites with irregular shapes. Mössbauer spectra of milled powders carried out at 297 and 77 K are well modeled with a histogram distribution of hyperfine fields. The presence of one additional sextet which corresponds to the ∝-Fe phase is also determined in agreement with XRD data analysis. Magnetic measurements suggest the suppression of the Morin transition in the milled samples and the absence of thermal relaxation effects in agreement with the Mössbauer spectroscopy results. © 2013 Springer Science+Business Media Dordrecht.