The crystal structure of the title compound, α-PbTeO(3) (PTO), has been reported previously by Mariolacos [Anz. Oesterr. Akad. Wiss. Math. Naturwiss. Kl. (1969), 106, 128-130], refined on powder data. The current determination at room temperature from data obtained from single crystals grown by the Czochralski method shows a significant improvement in the precision of the geometric parameters when all atoms have been refined anisotropically. The selection of a centrosymmetric (C2/c) structure model was confirmed by the second harmonic generation test. The asymmetric unit contains three formula units. The structure of PTO is built up of three types of distorted [PbO(x)] polyhedra (x = 7 and 9) which share their O atoms with TeO(3) pyramidal units. These main anionic polyhedra are responsible for establishing the two types of tunnel required for the stereochemical activity of the lone pairs of the Pb(2+) and Te(4+) cations.