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Polyoxometalates(POMs)are molecular metal oxides having rich electronic properties.POM-based materials with potential application in artificial photosynthesis and photo-catalysis have a number of features: POMs with numerous structure types can act as electron banks in which electrons are delocalized over large size ranges; POMs can accept and release electrons without structural changes; POMs can act as semiconductors with tunable band gaps.Covalently modified POM hybrids made of organic moieties grafted directly to a molecular metal-oxide core combine the electronic and architectural properties of POMs with the immense variability of organic chemistry.The organic parts can aid in adhering the POMs to surfaces,confer new electronic properties to the POMs or potentially form organic conducting materials incorporating POM side-chains.This talk presents a set of reactions to affix the organic moieties to the POM via specific functional groups for the desired properties.