This review is intended to provide an up-to-date and comprehensive description of recent advances since the mid-2010s in the elaboration and the involvement of polyoxometalates (POMs)-functionalized (photo)electrodes in (photo)electrocatalytic reactions. Focus has been essentially placed not only on reactions of high interest, such as hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and CO2 reduction reaction (CDRR) but also on other more "confidential" reactions (e.g., reduction of oxyanionic species and ascorbic acid oxidation). It is now well-known that POMs represent one class of fascinating compounds largely explored in inorganic chemistry, highlighted by the large number of complexes with structural, redox, and functional diversities which make them particularly attractive as efficient electrocatalysts for a wide range of significant multiredox reactions. The transposition of homogeneous electrocatalysis to (photo)electrode-supported electrocatalysis using POMs and its derivatives undoubtedly constitutes a really promising avenue toward the development of modern electrochemical devices, which could be of high interest for applications in chemical sensing, biosensing, electroanalysis, and solar-driven fuel cells.