Polyoxometalate (POM) based supramolecular assemblies have received significant attention over recent years because of their unique and diverse redox and photochemical behaviour and their potential value across a range of important light driven applications such as photo-driven synthesis and photocatalysis. This review explores the dominant approaches to assembly of polyoxometalates into supramolecular materials, both covalent and electrostatic, with particular focus on charge transfer materials and those capable of sensitized photoelectrocatalysis. The integration of POMs as components in devices such as dye sensitized solar cells, electrocatalytic photoanodes, sensing and waste remediation are considered. (C) 2015 Elsevier B.V. All rights reserved.