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Polyoxometalate-based metal–organic frameworks (PMOFs) as extended solids assembled from metal-oxide cluster units and metal–organic groups have drawn wide research attention in recent years due to the unique advantages of containing both polyoxometalate (POM) and metal–organic framework (MOF) units, which allow their multifunctional applications in catalysis, sensing, and energy storage. In this review, the recent progress on the syntheses, structural diversity, and potential applications of PMOFs are summarized. In terms of structure, two categories of PMOFs, POM@MOFs and POM–MOFs, are discussed. POM@MOFs are PMOFs in which the POM units are not coordinated to the MOF, whereas POM–MOFs are PMOFs in which the POM units are coordinated to the MOF. In terms of properties, some selected investigations on the application of PMOFs in catalysis, dye adsorption and degradation, chemical sensing and energy storage are covered. To conclude, a personal outlook and viewpoints on this field are presented. It is expected that this review will inspire researchers and provide helpful tips for the future rational design of function-oriented PMOFs.
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