Molecular metal oxides(Polyoxometalates,POMs)have outstanding chemical and physical properties,playing important roles in constructing novel functional materials.While conventional POMs are made of PO43-,SO42-,SiO42-etc redox silent templates,POMs based on redox-active templates are of more interests since the later have more diverse structure types and redox activities,more promising in materials applications.In this contribution,we present the approach of encapsulating nonconventional redox-active templates,including SO32-,SeO32-,TeO32-,TeO66-,IO3-and IO65-etc,to isolate new functional POMs from non-equilibrium systems.The experiments for optimizing reaction condition have been systematically investigated and x-ray single crystal structure determination,high resolution mass spectrometry,183W,77Se and 31P NMR,electrochemistry and electron paramagnetic resonance,etc have been applied for product characterization.The electronic and semi-conductive properties and application in electronic device of the novel POMs were preliminarily tested.