Presented herein is an example of the conversion of an aluminum oxo cluster (AlOC) to an aluminum oxo cluster organic cage (AlOCOC). We successfully synthesized the first example of an aluminum cluster-based organic cage-Al₁₂ tetrahedral cage via an Al₃ cluster. The use of 4-pyrazolecarboxylic acid plays an important role in the construction of the organic cage. Due to the presence of partially deprotonated ligands, the hydrogen-bonding interactions between the discrete tetrahedra generate porous supramolecular structures. Considering the high porosity and the abundant N–H sites, we further investigated the performance of the material towards iodine capture.