Only the orthorhombic form of lead meta-niobate (PbNb2O6 or PNO) is ferroelectric, allowing high temperature piezoelectric applications. Quenching from a high temperature like 1270 degrees C appears essential to get the orthorhombic phase. But such quenching is risky and can generate defects in the sample. Here, differential scanning calorimetry (DSC) and XRD characterizations show that on using suitably pre-fired Nb2O5 or monoclinic Nb2O5 as starting reactant, slow cooling as well as quenching leads to orthorhombic PbNb2O6 as the product. Present work is the first detailed report of the preparation of orthorhombic PbNb2O6 without quenching. All starting materials, tried here, and resulting products have been thermally characterized along with necessary XRD characterizations. (C) 2014 Elsevier B.V. All rights reserved.