Solar thermal water splitting ( STWS ) produces renewable hydrogen from water using concentrated sunlight. Because it utilizes energy from the entire solar spectrum to directly drive the redox reactions that split water, it can achieve high theoretical solar‐to‐hydrogen efficiencies. In two‐step STWS , a metal oxide is first heated by concentrated sunlight to high temperatures to reduce it and produce O 2 . In the second step, the reduced material is exposed to H 2 O to reoxidize it to its original oxidation state and produce H 2 . Various aspects of this process are reviewed in this work, including the reduction and oxidation chemistries of the active redox materials, the effects of operating conditions, and the solar thermal reactors in which the STWS reactions occur, and a perspective is given on the future optimization of STWS . WIREs Energy Environ 2016, 5:261–287. doi: 10.1002/wene.174 This article is categorized under: Concentrating Solar Power > Science and Materials Energy and Climate > Science and Materials Energy Research & Innovation > Science and Materials