In the field of polyoxometalate (POM) chemistry, organophosphonate covalently modified polyoxometalates (OCMPs) have recently emerged as a promising frontier. These hybrid materials not only broaden the structural diversity of conventional POM derivatives and address the inherent stability limitations of POMs, but also allow for the design of improved properties tailored to diverse applications. Despite this growing interest, a systematic review dedicated to OCMPs is still lacking. This review provides a comprehensive summary of recent advances in OCMP research, with a particular focus on their structural features, functional properties, and prospective research directions.