In view of its unique photocatalytic properties, decatungstate (W(10)O(32)(4-)) is rapidly emerging as a promising tool in organic chemistry. This tutorial review surveys recent developments in the chemistry of decatungstate, including mostly synthetic, and to a lesser extent mechanistic aspects. We have chosen to present several representative examples that illustrate the diverse uses of decatungstate in organic synthesis. Thus, the decatungstate-mediated radical functionalization of several classes of organic compounds such as alkanes, alkenes, alcohols, aldehydes and sulfides, under both aerobic and anaerobic conditions, represents reactions of fundamental and practical interest in academia and industry. Several new discoveries concerning the heterogenization of decatungstate for the development of sustainable methods with broad applications in catalysis, such as the photooxidation or photodegradation of various organic substrates, are also presented.