Further investigation reveals that at each defect vertex site, additional cuprophilic interactions with three adjacent Cu atoms from neighboring facets disrupt the regular geometries of the adjacent shells. More specifically the rhombicuboctahedron shell is formed by connecting eight triangular Cu frames, each maintaining a fixed distance from the vertex Cu atoms of the Cu8 cubic core. However, at the defect sites, we observed a change in the interaction of these triangular Cu frames. In the Cu58-I NC, this distance extends to 3.0016 Å, while the average distance at the other ends is 2.8766 ± 0.0319 Å. For the Cu58-II NC, this distance extends to 3.0253 ± 0.0099 Å, with the average distance at the other ends being 2.8876 ± 0.0464 Å (Figure ). Additionally, there is an observed alteration in the interatomic distances between these triangular Cu frames and the surrounding vertices of the Cu8 cubic core (Figure ). We noted a reduction in the average distance at the defect sites compared to the regular sites for both NCs. The shorter interatomic distances indicate an associated inward displacement strain of the triangular Cu frames, generated by the dislocation of the Cu atom in the outermost cationic shell. Consequently, the rhombicuboctahedron shell of both NCs experiences distortions, spreading to the nearby edge centers contributed by the Cu12 cuboctahedron shell. We found that the distances between the edge-center Cu atoms on each constituent vertex can be categorized into two groups. For the defective sides, the distances between the three adjacent edge-centers are approximately 6.2292 ± 0.0004 Å, while the distances between the edge-centers on the remaining vertices average 5.878 ± 0.0377 Å for Cu58-I NC. For Cu58-II NC, the distances are 6.2411 ± 0.0227 Å and 5.8269 ± 0.0434 Å, respectively (Figure ). These observations clearly demonstrate the impact of the distortion of the outer Cu(I) atoms on the inner shell geometry. On the other hand, this surface ligand vacancy directly exposes the defective vertex Cu atoms and indirectly exposes several neighboring facets and edges of these cubic NCs. Notably, the outward orientation of the edgecenter Cu atoms relative to others presents intriguing possibilities, as these edge-center atoms, along with the vertex Cu atom at the defect sites, may potentially serve as catalytic sites (Figure ). However, the distances between these atoms vary because the vertex-to-vertex distances change during the formation of the defect-induced structural architecture, which may uniquely affect their catalytic properties (Figure ).