Catalytic water oxidation represents a bottleneck for developing artificial photosynthetic systems that store solar energy as renewable fuels. A variety of molecular water oxidation catalysts (WOCs) have been reported over the last two decades. In view of their applications in artificial photosynthesis devices, it is essential to immobilize molecular catalysts onto the surfaces of conducting/semiconducting supports for fabricating efficient and stable water oxidation anodes/photoanodes. Molecular WOC-based anodes are essential for developing photovoltaic artificial photosynthesis devices and, moreover, the performance of molecular WOC on anodes will provide important insight into designing extended molecular WOC-based photoanodes for photoelectrochemical (PEC) water oxidation. This Review concerns recent progress in the development of molecular WOC-based anodes over the last two decades and looks at the prospects for using such anodes in artificial photosynthesis.