Compounds with the LiNbO3-type structure are important for a variety of applications, such as piezoelectric sensors, while recent attention has been paid to magnetic and electronic properties. However, all the materials reported are stoichiometric. This work reports on the high-pressure synthesis of lithium tungsten bronze LixWO3 with the LiNbO3-type structure, with a substantial non-stoichiometry (0.5 ≤ x ≤ 1). Li0.8WO3 exhibit a metallic conductivity. This phase is related to an ambient-pressure perovskite phase (0 ≤ x ≤ 0.5) by the octahedral tilting switching between a−a−a− and a+a+a+.
