This study presents a significant advancement in the synthesis and structure of dia topological exohedral metallofullerene (ExMF) frameworks based on cuprofullerene carboxylates. The C60@Cu4 cuprofullerene unit reveals unprecedented Cu2-based inherently chiral coordination modes. Theoretical analyses illuminate that the calculated bandgap is 0.91 eV, the valence band maximum (VBM) is dominated by 3d orbitals of Cu(I) atoms and 2p orbitals of C atoms from anthracene fragments, and the conduction band minimum (CBM) is by 2p orbitals of C atoms from C60, consistent with the calculation results of electron density difference (EDD) maps and the frontier orbitals. This work not only enriches the understanding of structural diversity of cuprofullerenes but also opens new avenues for the development of ExMF frameworks, holding potential for innovative applications in materials science and technology.