Orthorhombic phase of lead metaniobate (PbNb₂O₆) is piezoelectric with a high Curie temperature (>570°C) with high potential of wide use in important high temperature applications that cannot be covered by the popular piezoelectric materials based on BT and PZT. Difficulty of preparing it in pure phase hindered full characterisation and wide use of this long known piezoelectric material. Here,PbNb₂O₆ pellets have been prepared in pure orthorhombic phase and first characterised by room temperature TEM and XRD techniques, with a satisfying agreement of the two results. Next, we carried out high temperature x-ray diffraction study of its ferroelectric to paraelectric phase transition on heating across the Curie temperature, and also trace the cooling path.On heating the sample to 590°C and cooling back, there is a significant increase of cell volume.