Mesoporous metal phosphonates have received increasing attention as promising heterogeneous catalysts due to their abundant framework compositions and controllable porosity.
Catalysis is crucial for sustainable process management. The discovery of mesoporous metal phosphonate hybrid materials has opened great opportunities for new applications in catalysis, thanks to their homogeneous composition, combined merits of inorganic units and organic groups, and considerable porosity. In this review, we present the fundamentals of designing and optimizing hybrid mesostructures and the recent progress in the fields of metal phosphonate-based catalytic reactions. The catalytic reactions are divided into three categories based on the following elements, i.e., metal sites, organophosphonate moieties, and potential precursors of active metal phosphates. Each section highlights recent advances and the corresponding reactions are discussed in detail. Direct functionalization of the mesopore surfaces of the hybrids, such as sulfonation and supporting, features an elegant way to bridge the gap between heterogeneous and homogeneous catalysis. Moreover, remarks on the challenges and perspectives are presented for further exploration of mesoporous metal phosphonate hybrid heterogeneous catalysts.