The role of polyoxometalates (POMs) in the synthesis and stabilization of gold nanoparticles (Au NPs) is reviewed in light of many of the recent developments. The vitality of these hybrid materials is discussed with many examples of POMs and different synthesis techniques. Also, applications of these newly emerging hybrid materials in numerous fields such as electrocatalysis, photocatalysis, biomass catalysis, oxidation of alkenes, bio-sensing, and medicinal use are highlighted. Limitations in these applications are indicated, and areas of future applications that could be explored in these vast ranging hybrid materials are described.