Abstract An amorphous salt was precipitated by reacting barium bromide with a solution of peroxo-polytungstic acid. Heating it in a hydrogen stream at temperature near 550 °C yielded a hexagonal form of barium tungsten bronze, Ba x WO 3, in a pure phase with x being in the range 0.19–0.24. At temperature higher than 620 °C, this metastable compound was transformed into the tetragonal bronze phase. An unreported lead tungsten bronze in the hexagonal form ( a = 7.407, c = 7.565 A ̊ , for Pb 0.29WO3) was synthesized similarly but at lower temperature (420 °C). Their crystal structures were refined by the Rietveld method. The electric properties of the compounds were also investigated between 4.2 K to room temperature.