To achieve such global delocalization, non-benzenoid rings must be employed as the structural backbone. Porphyrinoids are a prominent class of π-conjugated functional molecules known for their facile redox interconversions and exceptional optical and magnetic properties, attributed to their highly delocalized π-electrons. Additionally, the conformational flexibility of expanded porphyrins enables them to adopt unusual topologies, making them versatile platforms for achieving diverse electronic states. For example, expanded porphyrins with half-twisted could exhibit [4N] Möbius aromaticity. Their structural diversity and effective electron delocalization also facilitate the investigation of aromaticity at three dimensions. Our group has demonstrated that porphyrinoid-based 3D fully π-conjugated molecular cages exhibit 3D global aromaticity, explained by the 2D Hückel/Baird aromaticity of their constitutional macrocycles in singlet/triplet states. Shinokubo's group further revealed that closely stacked antiaromatic porphyrinoid dimers can induce strong through-space frontier orbital interactions, forming a unique type of 3D aromaticity. Thus, porphyrinoids are ideal candidates for constructing MIMs with fully delocalized π-electrons, enabling distinctive electronic and magnetic interactions between the entangle rings. In this context, we report a fully π-conjugated [2]catenane (1) comprising two intertwined, core-modified octaphyrinoid rings, each forming a 34π-electron aromatic pathway (Fig. ). Four-electron oxidation yields a tetracation (1⁴⁺) with two 32π-electron antiaromatic rings. Detailed investigations into the aromaticity, geometry, and through-space electronic and magnetic interactions in both neutral and charged states reveal a dynamic interplay between molecular topology, electronic structure, and external factors-distinct from those observed in previously reported MIMs.