The paper presents the experimental results showing that the crystalline phase of the nano-particles, synthesized in a DC transferred arc thermal plasma reactor, critically depend on the operating pressure in the reaction zone. The paper reports about the changes in crystalline phases of three different compounds namely: aluminium oxide (Al2O3), aluminium nitride (AlN) and iron oxide (FexOy) synthesized at 760 Torr and 500 Torr of operating pressures. The major outcome of the present work is that the phases having higher defect densities are more probable to form at the sub-atmospheric operating pressures. The variations in the crystalline structures are discussed on the basis of the change in the temperature during the nucleation process, prevailing at the boundary of the plasma, on account of the ambient pressures. The as-synthesized nano-particles were examined by X-ray diffraction analysis and transmission electron microscopy. In addition, the confirmatory analysis of the crystalline phases of iron oxides was carried out with the help of Mossbauer spectroscopy. (C) 2008 Elsevier Ltd. All rights reserved.