The scope of this article is to reveal the fruitful combination of POM species with metal coordination complexes, leading to the construction of several efficient multifunctional catalysts. In this review, we try to underscore various catalytic and photocatalytic reactions catalyzed by POM‐based inorganic‐organic hybrid. Notably, it has been well established that depending on the type of the reaction, the activity and selectivity of these hybrid catalyst can be drastically improved by the rational and correct choice of the organic metal complex and POM anion providing a marriage of convenience.