The chemistry of organoimido derivatives of polyoxometalates (POMs) has received increasing interest. In recent decades, a great development of the synthetic chemistry of organoimido derivatives of POMs using different imido-releasing reagents has taken place, particularly the novel DCC-dehydrating protocol to prepare organoimido derivatives of POMs was developed recently by us and co-workers. Organoimido substituted POMs as valuable building blocks can construct novel nanostructured organic-inorganic hybrid molecular materials in well-developed common organic synthesis methods, such as Pd-catalyzed carbon-carbon coupling and esterification. Therefore, the reactive chemistry of organoimido derivatives of POMs stands for the fascinating future of the chemistry of organoimido derivatives of POMs.