Insertion of molecular metal oxides, e.g. polyoxometalates (POMs), into metal-organic frameworks (MOFs) opens up new research opportunities in various fields, particularly in catalysis. POM/MOF composites have strong acidity, oxygen-rich surface, and redox capacity due to typical characteristics of POMs and the large surface area, highly organized structures, tunable pore size, and shape are due to MOFs. Such hybrid materials have gained a lot of attention due to astonishing structural features, and hence have potential applications in organic catalysis, sorption and separation, proton conduction, magnetism, lithium-ion batteries, supercapacitors, electrochemistry, medicine, bio-fuel, and so on. The exceptional chemical and physical characteristics of POMOFs make them useful as catalysts in simple organic transformations with high capacity and selectivity. Here, the thorough catalytic study starts with a brief introduction related to POMs and MOFs, and is followed by the synthetic strategies and applications of these materials in several catalytic organic transformations. Furthermore, catalytic conversions like oxidation, condensation, esterification, and some other types of catalytic reactions including photocatalytic reactions are discussed in length with their plausible catalytic mechanisms. The disadvantages of the POMOFs and difficulties faced in the field have also been explored briefly from our perspectives.