Polyoxometalates (POM) have a rich and promising photochemical behavior. Upon illumination at the O M CT band (i.e., in UV and near-visible area) become powerful oxidizing reagents able to oxidize various organic compounds. In the process POM undergo stepwise reduction accumulating electrons that can be subsequently delivered, via thermal reactions to a variety of oxidants. This way a great variety of organic compounds are oxidized and indeed mineralize to CO2, H2O and inorganic anions and several organic and inorganic compounds can be reduced via a photocatalytic process in which POM serve as electron relays. Thus, in principle, POM can serve as decontamination photocatalysts of aquatic media removing both organic pollutants and metal ions. Under special conditions controlled photocatalytic reactions have been reported. In addition the reduction precipitation of metal ions mediated by POM may lead to formation of metal nanoparticles in which POM serve as reducing reagents and stabilizers.