In summary, this work validates the potential of aluminum molecular rings as building blocks for high-connectivity COFs and expands their utility into photocatalysis. This study represents the first breakthrough in integrating aluminum molecular rings into covalent networks. This advancement paves a new way for novel multidimensional network designs based on aluminum molecular rings. It is reasonable to expect such ring units to enable access to richer network structures and topologies, offering new structural paradigms for high-connectivity functional frameworks. The pre-organized aluminum molecular rings exhibit notable advantages, including low cost, high stability, and structural tailorability, providing a robust foundation for advancing MCCOF applications. Future research could further propel this field by employing precise functionalization strategies to tailor aluminum molecular rings with specific properties. Potential directions include, but are not limited to, the following aspects: 1) Precise control over the ring size. Introducing macrocyclic structures can significantly enhance the porosity of MCCOFs and facilitate the construction of hierarchical pore systems, showing promising potential for applications in gas adsorption and molecular sieving. 2) Rational design the pore microenvironments. Incorporation of specific heteroatoms (O, F or S) could not only impart functional properties such as proton conduction and sensing but also enable the modulation of physicochemical behaviors via encapsulation of functional guest species. 3) Functionalization of the surface chemistry. By selecting diverse functional ligands and controlling their spatial arrangement, more versatile functionalities of MCCOF materials would be unlock. For instance, the introduction of chiral or photoactive ligands may expand applications in chiral recognition, information storage, catalysis and optoelectronic properties.